Composition for forming lithographic film, method for forming resist pattern, and method for forming circuit pattern

Abstract

To provide a lithographic film-forming composition capable of forming a resist pattern with high resolution and reduced roughness.SOLUTION: A composition for forming a lithographic film, comprising at least one selected from a compound having a predetermined structure and a resin obtainable by using the compound as a monomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a lithographic film, a method for forming a resist pattern, and a method for forming a circuit pattern. [Background technology]

[0002] In the manufacture of semiconductor devices, microfabrication is carried out by lithography using photoresist materials, but in recent years, with the increasing integration and speed of LSI (large-scale integrated circuits), further miniaturization using pattern rules is required. In addition, the light source for lithography used in forming resist patterns has been shortened in wavelength from KrF excimer laser (248 nm) to ArF excimer laser (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) is also expected.

[0003] However, in lithography using conventional polymer resist materials, the molecular weight is large, on the order of 10,000 to 100,000, and the molecular weight distribution is wide, which causes roughness on the pattern surface, making it difficult to control the pattern dimensions and limiting miniaturization. Therefore, various low-molecular-weight resist materials have been proposed to provide resist patterns with higher resolution. Because low-molecular-weight resist materials have small molecular sizes, they are expected to provide resist patterns with high resolution and low roughness.

[0004] Currently, various low-molecular-weight resist materials are known. For example, alkali-developable negative-tone radiation-sensitive compositions using a low-molecular-weight polynuclear polyphenol compound as a main component have been proposed (see, for example, Patent Document 1 and Patent Document 2). As a candidate for a low-molecular-weight resist material with high heat resistance, alkali-developable negative-tone radiation-sensitive compositions using a low-molecular-weight cyclic polyphenol compound as a main component have also been proposed (see, for example, Patent Document 3 and Non-Patent Document 1). Furthermore, it is known that polyphenol compounds, as base compounds of resist materials, can impart high heat resistance despite their low molecular weight and are useful for improving the resolution and roughness of resist patterns (see, for example, Non-Patent Document 2).

[0005] Furthermore, Patent Document 4 proposes a resist composition containing a compound of a specific structure and an organic solvent as a material that has excellent etching resistance, is soluble in a solvent, and is applicable to a wet process.

[0006] Furthermore, as resist patterns become finer, problems arise, such as resolution issues (low resolution making it difficult to form a suitable pattern) or resist pattern collapse after development (when the resist has low rigidity, resistance to pattern collapse during development is reduced, causing the resist pattern to collapse (or become wavy)). Therefore, thinner resist films are desired. However, simply thinning the resist makes it difficult to obtain a resist pattern with a film thickness sufficient for substrate processing. Therefore, there is a demand for a process that not only forms a resist pattern, but also creates an underlayer film between the resist and the semiconductor substrate to be processed, and allows this underlayer film to function as a mask during substrate processing. Furthermore, processes have been put into practical use that increase the etching resistance of the resist to reduce the required film thickness, or that transfer the resist pattern to an underlayer film between the resist and the semiconductor substrate to be processed, thereby providing this underlayer film with high etching resistance and photosynthetic functionality.

[0007] Currently, various underlayer films for lithography are known. For example, a material for forming an underlayer film for a multilayer resist process containing a resin component having at least a substituent that generates a sulfonic acid residue by elimination of an end group upon application of a predetermined energy, and a solvent, has been proposed to realize a resist underlayer film with a dry etching rate selectivity similar to that of a resist, unlike conventional underlayer films with a high etching rate (see, for example, Patent Document 5). Furthermore, a material for forming an underlayer film for lithography with a dry etching rate selectivity lower than that of a resist has been proposed, containing a polymer having a specific repeating unit (see, for example, Patent Document 6). Furthermore, a material for forming a resist underlayer film for lithography with a dry etching rate selectivity lower than that of a semiconductor substrate has been proposed, containing a polymer obtained by copolymerizing a repeating unit of an acenaphthylene derivative with a repeating unit having a substituted or unsubstituted hydroxy group (see, for example, Patent Document 7).

[0008] On the other hand, amorphous carbon underlayer films formed by chemical vapor deposition (CVD) using methane gas, ethane gas, acetylene gas, etc., are well-known as materials with high etching resistance for this type of resist underlayer film. However, from a process perspective, there is a demand for resist underlayer film materials that can be formed by wet processes such as spin coating and screen printing.

[0009] Furthermore, Patent Document 8 describes a material for forming an underlayer film for lithography that contains a compound with a specific structure, and that has excellent etching resistance, high heat resistance, is soluble in a solvent, and is applicable to wet processes.

[0010] Known methods for forming an intermediate layer used in forming a resist underlayer film in a three-layer process include a method for forming a silicon nitride film (see, for example, Patent Document 9) and a CVD method for forming a silicon nitride film (see, for example, Patent Document 10). Also, known intermediate layer materials for a three-layer process include materials containing silsesquioxane-based silicon compounds (see, for example, Patent Documents 11 and 12). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-326838 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-145539 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-173623 [Patent Document 4] International Publication No. 2013 / 024778 [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-177668 [Patent Document 6] Japanese Patent Application Laid-Open No. 2004-271838 [Patent Document 7] Japanese Patent Application Laid-Open No. 2005-250434 [Patent Document 8] International Publication No. 2013 / 024779 [Patent Document 9] Japanese Patent Application Laid-Open No. 2002-334869 [Patent Document 10] International Publication No. 2004 / 066377 [Patent Document 11] Japanese Patent Application Laid-Open No. 2007-226170 [Patent Document 12] Japanese Patent Application Laid-Open No. 2007-226204 [Non-patent literature]

[0012] [Non-Patent Document 1] T.Nakayama,M.Nomura,K.Haga,M.Ueda:Bull.Chem.Soc.Jpn.,71,2979(1998) [Non-patent document 2] Shinji Okazaki and 22 others, "New Developments in Photoresist Material Development," CMC Publishing Co., Ltd., September 2009, pp. 211-259 Summary of the Invention [Problem to be solved by the invention]

[0013] However, the materials described in Patent Documents 1 to 12 and Non-Patent Documents 1 and 2 still have room for improvement in terms of simultaneously satisfying high levels of solubility in organic solvents, heat resistance, etching resistance, and resist pattern formability as film-forming materials for lithography. Furthermore, there is also room for improvement in terms of simultaneously satisfying high levels of solubility in organic solvents, storage stability and thin film formability, etching resistance, sensitivity, and resist pattern formability as film-forming materials for lithography in a balanced manner.

[0014] The present invention has been made in view of the problems associated with the above-mentioned conventional techniques, and aims to provide a composition for forming a lithography film, a method for forming a resist pattern, and a method for forming a circuit pattern, which are useful for forming a lithography film. [Means for solving the problem]

[0015] As a result of extensive research to solve the above problems, the present inventors have discovered that a composition containing a compound having a specific structure is useful for forming a lithography film, and have thus completed the present invention.

[0016] That is, the present invention includes the following aspects. [1] A composition for forming a lithographic film, comprising at least one compound selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (3), a compound represented by formula (4), a compound represented by formula (5), and a resin obtained using these as a monomer. [ka] (In the formula, each R independently represents an aromatic group having 6 to 36 carbon atoms which may have a substituent or a heteroatom, X's each independently represent an alkanediyl group having 2 to 4 carbon atoms or an alkanediylcarbonyl group having 1 to 4 carbon atoms, each of which may have a substituent; P's each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, each of which may have a substituent, or a hydrogen atom, a crosslinkable group, or a dissociable group; Each m independently represents an integer of 1 to 6, and each n independently represents an integer of 0 to 4. [ka] (In the formula, each R independently represents an aromatic group having 6 to 36 carbon atoms which may have a substituent or a heteroatom, R c each independently represents a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, or an arylene group having 1 to 20 carbon atoms which may have a substituent, X's each independently represent an alkanediyl group having 2 to 4 carbon atoms or an alkanediylcarbonyl group having 1 to 4 carbon atoms, each of which may have a substituent; P's each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, each of which may have a substituent, or a hydrogen atom, a crosslinkable group, or a dissociable group; Each m independently represents an integer of 1 to 6, and each n independently represents an integer of 0 to 4. [ka] (In formula (4), Each A independently represents an aromatic group having 6 to 10 carbon atoms; each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group; R 1 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Each Rx1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; Ry1's each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; m represents an integer of 0 to 4, and n represents an integer of 0 to 4. [ka] (In formula (5), Each A independently represents an aromatic group having 6 to 10 carbon atoms; each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group; R 2 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Each Rx2 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; Ry2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; m represents an integer of 0 to 4, and n represents an integer of 0 to 4. [2] The composition for forming a lithographic film according to [1], wherein the compound represented by the general formula (1) is a compound represented by the general formula (2): [ka] (In the formula, R, X, P, and n are defined as in formula (1).) [3] The composition for forming a lithographic film according to [1], which contains a compound represented by the general formula (3). [4] The composition for forming a lithographic film according to [1], comprising at least one selected from the group consisting of a compound represented by formula (4), a compound represented by formula (5), and a resin obtained using these as a monomer. [5] The compound represented by formula (4) is a compound represented by formula (6), The composition for forming a lithographic film according to [4], wherein the compound represented by formula (5) is a compound represented by formula (7). [ka] (In formula (6), P, R 1 , Rx1, Ry1, m, and n have the same meanings as in formula (4). [ka] (In formula (7), P, R 2 , Rx2, Ry2, m, and n are defined as in formula (5). [6] The composition for forming a lithographic film according to [4], wherein the resin is a resin represented by formula (8): [ka] (In formula (8), B is a structural unit derived from a compound represented by formula (4) and / or a structural unit derived from a compound represented by formula (5), L is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, or an arylene group having 1 to 20 carbon atoms which may have a substituent, When there are a plurality of B and / or L, they are independent of each other. [7] The composition for forming a lithographic film according to any one of [1] to [6], further comprising a solvent. [8] The composition for forming a lithographic film according to any one of [1] to [7], further comprising an acid generator. [9] The composition for forming a lithographic film according to any one of [1] to [8], further comprising a crosslinking agent.

[10] a photoresist layer forming step of forming a photoresist layer on a substrate using the composition for forming a lithographic film according to any one of [1] to [9]; a developing step of irradiating predetermined regions of the photoresist layer with radiation and developing the layer to obtain a resist pattern; A method for forming a resist pattern, comprising:

[11] The method for forming a resist pattern according to

[10] , wherein the resist pattern is an insulating film pattern.

[12] a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition for lithography film formation according to any one of [1] to [9]; a photoresist layer forming step of forming at least one photoresist layer on the resist underlayer film; a developing step of irradiating predetermined regions of the photoresist layer with radiation and developing the layer to obtain a resist pattern; A method for forming a resist pattern, comprising:

[13] a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition for lithography film formation according to any one of [1] to [9]; an intermediate layer film forming step of forming an intermediate layer film on the resist underlayer film; a photoresist layer forming step of forming at least one photoresist layer on the intermediate layer film; a resist pattern forming step of irradiating predetermined regions of the photoresist layer formed in the photoresist layer forming step with radiation and developing the photoresist layer to obtain a resist pattern; an intermediate layer film pattern forming step of etching the intermediate layer film using the resist pattern as a mask to obtain an intermediate layer film pattern; a resist underlayer film pattern formation step of etching the resist underlayer film using the intermediate layer film pattern as a mask to obtain a resist underlayer film pattern; a substrate pattern forming step of etching the substrate using the resist underlayer film pattern as a mask to obtain a substrate pattern; A circuit pattern forming method comprising: [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a lithography film-forming composition that is useful for forming a lithography film that is excellent in heat resistance, etching resistance, and resist pattern formability, as well as a resist pattern formation method and a circuit pattern formation method using the same. Furthermore, according to the present invention, it is possible to provide a composition that is useful as a film-forming material for lithography, which has high solubility in organic solvents, excellent storage stability and thin-film formability, high etching resistance, high sensitivity, and excellent resist pattern formability, and which satisfies these physical properties in a well-balanced manner at a high level.Furthermore, by using this composition, it is possible to provide a method for forming a resist pattern and a method for forming a circuit pattern. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, an embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only the present embodiment.

[0019] In this specification, unless otherwise specified, the term "alkyl group" may be a linear or branched alkyl group or a cyclic alkyl group, and is used to encompass these. Similarly, the term "alkoxy group" may be a linear or branched alkoxy group or a cyclic alkoxy group, and is used to encompass these.

[0020] The lithography film-forming composition of this embodiment contains at least one selected from a compound represented by general formula (1), a compound represented by general formula (3), a compound represented by formula (4), a compound represented by formula (5), and a resin obtained using these as a monomer. The lithography film-forming composition of this embodiment containing at least one selected from a compound represented by general formula (1) and a compound represented by general formula (3) will be referred to as the first lithography film-forming composition, and the lithography film-forming composition of this embodiment containing at least one selected from a compound represented by general formula (3), a compound represented by formula (4), a compound represented by formula (5), and a resin obtained using these as a monomer will be referred to as the second lithography film-forming composition.

[0021] [First Lithography Film-Forming Composition] The first lithography film-forming composition of the present embodiment (hereinafter also referred to simply as the "first composition", and also referred to as the "composition" when not distinguished from the second lithography film-forming composition described later) contains a compound represented by the following formula (1) (hereinafter also referred to simply as "compound (1)") and / or a compound represented by the following formula (3) (hereinafter also referred to simply as "compound (3)"). [ka] In the formula, each R independently represents an aromatic group having 6 to 36 carbon atoms which may have a substituent or a heteroatom. Each X independently represents an alkanediyl group having 2 to 4 carbon atoms or an alkanediylcarbonyl group having 1 to 4 carbon atoms, which may have a substituent. Each P independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, each of which may have a substituent, or a hydrogen atom, a crosslinkable group, or a dissociable group. Each m independently represents an integer of 1 to 6. Each n independently represents an integer of 0 to 4. [ka] In the formula, each R independently represents an aromatic group having 6 to 36 carbon atoms which may have a substituent or a heteroatom. R c each independently represents a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, or an arylene group having 1 to 20 carbon atoms which may have a substituent. Each X independently represents an alkanediyl group having 2 to 4 carbon atoms or an alkanediylcarbonyl group having 1 to 4 carbon atoms, which may have a substituent. Each P independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, each of which may have a substituent, or a hydrogen atom, a crosslinkable group, or a dissociable group. Each m independently represents an integer of 1 to 6. Each n independently represents an integer of 0 to 4.

[0022] The first composition can provide a composition for forming a lithography film that is useful for forming a lithography film that is excellent in heat resistance, etching resistance, and resist pattern formability, as well as a method for forming a resist pattern and a method for forming a circuit pattern using the same.

[0023] Unless otherwise defined, the substituent shown in Compound (1) and Compound (3) of this embodiment means a group in which one or more hydrogen atoms in a functional group are substituted with an atom other than a hydrogen atom or a functional group. The number of substituents is not particularly limited and may be one or more. The substituent shown in compound (1) and compound (3) of this embodiment is not particularly limited, and examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms. The alkyl group may be a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group. Similarly to the alkyl group, the aryl group, the alkoxyl group, the alkenyl group, the alkynyl group, the acyl group, and the amino group may be linear, branched, or cyclic.

[0024] The first composition contains compound (1) and / or compound (3) of this embodiment, making it suitable for wet processes and providing excellent heat resistance and planarization properties. Furthermore, since the first composition contains compound (1) and / or compound (3), film degradation during high-temperature baking is suppressed, enabling the formation of a lithography film with excellent etching resistance to oxygen plasma etching and the like. Furthermore, the first composition also has excellent adhesion to resist films, enabling the formation of excellent resist patterns. Therefore, the first composition is used for the formation of lithography films.

[0025] In this embodiment, the term "lithography film" refers to a general term for a film used in a lithography process, and includes, for example, an upper layer film, a resist film, an intermediate film, a resist underlayer film, an anti-reflective film, and a permanent resist film. The upper layer film is disposed on top of the resist film and has, for example, water repellency, and the intermediate film can also be provided with various physical properties depending on its relative positional relationship with the resist film and the resist underlayer film. In addition to the above, examples of lithography films include films for filling in steps in a processed layer to achieve planarization. The composition of this embodiment can be used to preferably form a resist film or a resist underlayer film as a lithography film. That is, the resist film of this embodiment and the resist underlayer film of this embodiment are formed from the composition of this embodiment.

[0026] The above R preferably represents an aromatic group having 6 to 16 carbon atoms which may have a substituent or a heteroatom, and more preferably represents an aromatic group having 6 to 14 carbon atoms which may have a substituent or a heteroatom.

[0027] Above R c represents preferably a single bond, a linear or branched alkylene group having 1 to 3 carbon atoms, or an arylene group having 1 to 13 carbon atoms, and more preferably represents a group selected from a methylene group, a phenylmethylene group, a biphenylmethylene group, and a cyclohexylphenylmethylene group.

[0028] The above X preferably represents an alkanediyl group having 2 to 4 carbon atoms which may have a substituent, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethanediyl group.

[0029] The above P preferably represents a hydrogen atom, a crosslinkable group or a dissociable group.

[0030] In this embodiment, the term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but examples include alkyl groups having 1 to 20 carbon atoms that, together with the oxygen atom to which the P is bonded in the formula, form an alkoxy group having 1 to 20 carbon atoms. Other examples of the crosslinkable group include groups having an allyl group, groups having a (meth)acryloyl group, groups having an epoxy(meth)acryloyl group, groups having a hydroxyl group, groups having a urethane(meth)acryloyl group, groups having a glycidyl group, groups having a vinyl-containing phenylmethyl group, groups having various alkynyl groups, groups having a carbon-carbon double bond, and groups having a carbon-carbon triple bond. Furthermore, among groups containing these groups, groups that crosslink in the presence or absence of a catalyst are also included. The "group containing these groups" is preferably an alkoxy group represented by -ORx (Rx represents a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a hydroxyl group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, a group having a vinyl-containing phenylmethyl group, a group having various alkynyl groups, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, or a group containing these groups.) In this specification, when the functional groups (excluding crosslinkable groups) described above as constituting the compound of this embodiment overlap with crosslinkable groups, those that are not crosslinkable are functional groups, and those that are crosslinkable are crosslinkable groups, based on the presence or absence of crosslinkability.

[0031] The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a desoxy group, and an isokoxy group.

[0032] The group having an allyl group is not particularly limited, but examples thereof include groups represented by any of the following formulas (X-1).

[0033] [ka] In the formula, n X1 represents an integer of 1 to 5.

[0034] The group having a (meth)acryloyl group is not particularly limited, but examples thereof include groups represented by any of the following formulas (X-2).

[0035] [ka] In the formula, n X2 represents an integer of 1 to 5. R X represents a hydrogen atom or a methyl group.

[0036] The group having an epoxy(meth)acryloyl group is not particularly limited, but examples thereof include a group represented by the following formula (X-3): Here, the epoxy(meth)acryloyl group refers to a group generated by reaction of an epoxy(meth)acrylate with a hydroxyl group.

[0037] [ka] In the formula, n x3 represents an integer of 0 to 5, and preferably represents 0. R X represents a hydrogen atom or a methyl group, and preferably represents a methyl group.

[0038] The group having a hydroxyl group is not particularly limited, but examples thereof include groups represented by any of the following formulas (X-5).

[0039] [ka] In the formula, n x5 represents an integer of 1 to 5, and preferably represents 1.

[0040] The group having a urethane (meth)acryloyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-4).

[0041] [ka] In the formula, n x4 represents an integer of 0 to 5, and preferably represents 0. s represents an integer of 0 to 3, and preferably represents 0. R X represents a hydrogen atom or a methyl group, and preferably represents a methyl group.

[0042] The group having a glycidyl group is not particularly limited, but examples thereof include groups represented by any of the following formulas (X-6).

[0043] [ka] In the formula, n x6 represents an integer of 1 to 5.

[0044] The group having a vinyl-containing phenylmethyl group is not particularly limited, but examples thereof include groups represented by any of the following formulas (X-7).

[0045] [ka] In the formula, n x7 represents an integer of 1 to 5, and preferably represents 1.

[0046] The various groups having an alkynyl group are not particularly limited, but examples thereof include groups represented by any of the following formulas (X-8).

[0047] [ka] In the formula, n x8 represents an integer of 1 to 5.

[0048] Examples of the carbon-carbon double bond-containing group include a (meth)acryloyl group, a substituted or unsubstituted vinylphenyl group, and a group represented by the following formula (X-9-1): Furthermore, examples of the carbon-carbon triple bond-containing group include a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, a group represented by the following formula (X-9-2), and a group represented by the following formula (X-9-3):

[0049] [ka]

[0050] In the formula, R X9A , R X9B and R X9C are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0051] [ka]

[0052] [ka]

[0053] In the formula, R X9D , R X9E and R X9F are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0054] In this embodiment, the term "dissociable group" refers to a group that dissociates in the presence or absence of a catalyst. Among dissociable groups, an acid-dissociable group refers to a group that is cleaved in the presence of an acid and changes into an alkali-soluble group or the like.

[0055] The alkali-soluble group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group, and the like. Among these, from the viewpoint of easy availability of an introduction reagent, a phenolic hydroxyl group and a carboxyl group are preferred, and a phenolic hydroxyl group is more preferred.

[0056] The acid-dissociable group preferably has the property of undergoing a chain cleavage reaction in the presence of an acid, in order to enable highly sensitive and high-resolution pattern formation.

[0057] The acid-dissociable group is not particularly limited, but can be appropriately selected from those proposed for hydroxystyrene resins, (meth)acrylic acid resins, and the like used in chemically amplified resist compositions for KrF or ArF.

[0058] Specific examples of the acid-dissociable group include those described in WO 2016 / 158168. Examples of the acid-dissociable group include 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, silyl groups, acyl groups, 1-substituted alkoxymethyl groups, cyclic ether groups, alkoxycarbonyl groups (e.g., -C(O)OC(CH)), and alkoxycarbonylalkyl groups (e.g., -(CH) n Suitable examples include C(O)OC(CH3)3 where n = 1 to 4. In this specification, when the functional groups (excluding dissociative groups) described above as constituting the compound of this embodiment overlap with dissociative groups, those that are not dissociative are treated as corresponding to the respective functional groups, and those that are dissociative are treated as corresponding to the dissociative groups, based on whether they are dissociative or not.

[0059] The substituent substituted on the dissociative group is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, a cyano group, a nitro group, and a heteroatom.

[0060] The halogen atom is not particularly limited, but examples thereof include a chlorine atom, a bromine atom, and an iodine atom.

[0061] The alkyl group may be linear, branched, or cyclic. The alkyl group is not particularly limited, but examples thereof include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, a tert-butyl group, a cyclohexyl group, and an adamantyl group.

[0062] The aryl group is not particularly limited, but examples thereof include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group. The aryl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms.

[0063] The aralkyl group is not particularly limited, but examples thereof include a benzyl group, a phenethyl group, etc. The aralkyl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms.

[0064] Examples of alkynyl groups include, but are not limited to, ethynyl and propargyl groups.

[0065] The acyl group is not particularly limited, but examples thereof include aliphatic acyl groups having 1 to 6 carbon atoms, such as a formyl group or an acetyl group, and aromatic acyl groups, such as a benzoyl group.

[0066] The alkoxycarbonyl group is not particularly limited, but examples thereof include alkoxycarbonyl groups having 2 to 5 carbon atoms, such as a methoxycarbonyl group.

[0067] The alkyloyloxy group is not particularly limited, but examples thereof include an acetoxy group.

[0068] The aryloyloxy group is not particularly limited, but examples thereof include a benzoyloxy group.

[0069] Examples of heteroatoms include, but are not limited to, oxygen, sulfur, selenium, nitrogen, and phosphorus atoms. Heteroatoms may replace carbon atoms in each group.

[0070] The number of carbon atoms of each group described in this specification is the total number of carbon atoms including the above-mentioned substituents, if any.

[0071] The above m is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, even more preferably an integer of 1 or 2, and even more preferably 1.

[0072] When the m is 1, the compound (1) is a compound represented by the general formula (2) (hereinafter, also simply referred to as the compound (2)). [ka] In the formula, R, X, P, and n have the same meanings as in formula (1).

[0073] The above n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 from the viewpoint of heat resistance, and even more preferably 1 from the viewpoint of solubility.

[0074] Compound (1) can be used as it is as a material for forming an underlayer film for lithography. Compound (1) can also be used as an oligomerized resin obtained by polymerizing compounds (1) together or by reacting compound (1) with a crosslinkable monomer. An example of a resin obtained by oligomerizing compound (1) is the above-mentioned compound (3). Compound (1) as a monomer used for oligomerizing compound (3) may be one type or two or more types.

[0075] The compound (3) can be obtained by polymerizing the compound (1) alone or by reacting the compound (1) with a compound having crosslinking reactivity. The method for polymerizing compound (1) alone is not particularly limited, but for example, aromatic rings of compound (1) may be directly bonded to each other by one-electron oxidation polymerization in the presence of an oxidizing agent. In this case, R C indicates a single bond. The oxidizing agent is not particularly limited, but examples thereof include metal salts or metal complexes containing copper, manganese, iron, cobalt, ruthenium, chromium, palladium, etc.; peroxides such as hydrogen peroxide and perchloric acids; organic peroxides, etc. Among these, metal salts or metal complexes containing copper, manganese, iron, or cobalt are preferred. Metals contained in the metal salts, such as copper, manganese, iron, cobalt, ruthenium, chromium, and palladium, may function as oxidizing agents by being reduced in the reaction system.

[0076] The crosslinkable compound may be any compound capable of oligomerizing or polymerizing compound (1), and examples thereof include aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanate compounds, and unsaturated hydrocarbon group-containing compounds.

[0077] The compound (3) is not particularly limited, but examples thereof include novolak resins obtained by a condensation reaction between the compound (1) and aldehydes or ketones, which are crosslinkable compounds.

[0078] The aldehydes are not particularly limited as long as they are used when compound (1) is novolakized. The aldehydes may be used alone or in combination of two or more. In addition to the aldehydes, one or more ketones may also be used in combination. From the viewpoint of exhibiting high heat resistance, the aldehydes are at least one selected from the group consisting of benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. From the viewpoint of improving etching resistance, one or more selected from the group consisting of benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural are preferred, and formaldehyde is more preferred. The amount of the aldehydes used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, per 1 mol of compound (1).

[0079] The ketones are not particularly limited as long as they are those that can be used to novolakize compound (1). One type of ketone may be used alone, or two or more types may be used in combination. From the viewpoint of exhibiting high heat resistance, the ketones include cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, From the viewpoint of improving etching resistance, one or more selected from the group consisting of acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl are preferred. The amount of ketones used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, per mol of compound (1).

[0080] A catalyst can also be used in the condensation reaction of compound (1) with aldehydes or ketones. The acid catalyst or base catalyst used here can be appropriately selected from known catalysts and is not particularly limited. Examples of such acid catalysts and base catalysts are the same as those listed in the production method of compound (1). These catalysts can be used alone or in combination of two or more. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid are preferred from the viewpoint of production, such as ease of availability and ease of handling. The amount of acid catalyst used can be appropriately determined depending on the types of raw materials and catalysts used, as well as the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass per 100 parts by mass of the reaction raw materials.

[0081] When compound (3) is produced by copolymerization of compound (1) with a compound having a non-conjugated double bond, such as indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, or limonene, aldehydes and ketones do not need to be used.

[0082] A reaction solvent can also be used in the condensation reaction of compound (1) with an aldehyde or a ketone. The reaction solvent for this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples of the reaction solvent include water, methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol, tetrahydrofuran, dioxane, and mixtures thereof. These solvents can be used alone or in combination of two or more.

[0083] The amount of solvent used can be appropriately set depending on the raw materials and catalyst used, as well as the reaction conditions, and is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. Furthermore, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C. Examples of reaction methods include a method in which compound (1), aldehydes and / or ketones, and the catalyst are charged all at once, and a method in which compound (1), aldehydes and / or ketones are successively added dropwise in the presence of a catalyst.

[0084] After the polycondensation reaction is completed, the obtained resin can be isolated by a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts present in the system, the temperature of the reactor is increased to 130 to 230°C, and volatile matters are removed at about 1 to 50 mmHg, and by adopting a general method, the target product (for example, a novolak resin) can be obtained.

[0085] Compound (3) may be a homopolymer of compound (1), or may be a copolymer of compound (1) and a phenol other than compound (1). The copolymerizable phenols are not particularly limited, but examples thereof include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, propylphenol, pyrogallol, and thymol.

[0086] Compound (3) is polymerizable with compound (1) and may be copolymerized with a monomer other than the above-mentioned phenols (hereinafter also referred to as a "comonomer"). Examples of such copolymerizable monomers include, but are not limited to, naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinylnorbornaene, pinene, and limonene. Compound (3) may be a two- or more-component (e.g., two- to four-component) copolymer of compound (1) and the above-mentioned phenols, a two- or more-component (e.g., two- to four-component) copolymer of compound (1) and the above-mentioned copolymerizable monomers, or a three- or more-component (e.g., three- or four-component) copolymer of compound (1), the above-mentioned phenols, and the above-mentioned copolymerizable monomers.

[0087] The weight-average molecular weight (Mw) of compound (3) is not particularly limited, but is preferably 300 to 100,000, more preferably 500 to 30,000, and even more preferably 750 to 20,000, as calculated in terms of polystyrene by GPC measurement. From the viewpoints of increasing crosslinking efficiency and suppressing volatile components during baking, the polydispersity of compound (3) (weight-average molecular weight Mw / number-average molecular weight Mn) is preferably in the range of 1 to 7.

[0088] Compound (1) and compound (3) each preferably have high solubility in a solvent, from the viewpoint of facilitating the application of a wet process. More specifically, when propylene glycol monomethyl ether (hereinafter also referred to as "PGME") and / or propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA") is used as the solvent, compound (1) and compound (3) each preferably have a solubility of 10% by mass or more in the solvent. Here, the solubility in PGME and / or PGMEA is defined as "total mass of compound (1) and compound (3) ÷ (total mass of compound (1) and compound (3) + mass of solvent) × 100 (% by mass)." For example, a total mass of 10 g of compound (1) and compound (3) is evaluated as having high solubility in 90 g of PGMEA when the solubility of compound (1) and compound (3) in PGMEA is "10% by mass or more," and is evaluated as not having high solubility when the solubility is "less than 10% by mass." The above "total mass of compound (1) and compound (3)" refers to the mass of compound (1) when the first composition does not contain compound (3) but contains compound (1). Also, it refers to the mass of compound (3) when the first composition does not contain compound (1) but contains compound (3). The same applies hereinafter.

[0089] Specific examples of Compound (1) and Compound (3) include compounds represented by the following formulae: However, Compound (1) and Compound (3) are not limited to compounds represented by the following formulae.

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] In the formula, each OP' independently represents a crosslinkable group or a dissociable group.

[0095] [ka]

[0096] [Second Lithography Film-Forming Composition] The second lithography film-forming composition of this embodiment (hereinafter simply referred to as the "second composition") contains at least one selected from the group consisting of a compound represented by formula (4) (hereinafter also referred to as "compound (4)"), a compound represented by formula (5) (hereinafter also referred to as "compound (5)"), and a resin obtained using these as a monomer (hereinafter also referred to as a "resin"). Preferably, the compound represented by formula (4) is a compound represented by formula (6) (hereinafter also referred to as "compound (6)"), and the compound represented by formula (5) is a compound represented by formula (7) (hereinafter also referred to as "compound (7)"). In this embodiment, the compound represented by formula (4), the compound represented by formula (5), the compound represented by formula (6), the compound represented by formula (7), and the resin obtained using these as a monomer are also referred to as "compounds (4) to (7), and resins."

[0097] The second composition has high solubility in organic solvents, excellent storage stability and thin-film formability, high etching resistance, high sensitivity, and excellent resist pattern formability, and satisfies these physical properties in a well-balanced manner at a high level, making it possible to provide a composition useful as a film-forming material for lithography. Furthermore, by using this composition, it is possible to provide a method for forming a resist pattern and a method for forming a circuit pattern.

[0098] Compounds (4) to (7) and resins of this embodiment have a plurality of polar groups, and therefore have excellent solubility in organic solvents. In addition, compounds (4) to (7) and resins have a relatively high content of aromatic rings, and therefore have excellent crosslinking reactivity, and therefore also have the effect of excellent heat resistance. The second composition containing compounds (4) to (7) and a resin of this embodiment also has excellent solubility in organic solvents, is applicable to wet processes, and has excellent storage stability, thin-film formability, planarization properties, and heat resistance. Furthermore, the second composition can form a lithography film that is inhibited from deterioration during high-temperature baking and has excellent etching resistance to oxygen plasma etching and the like. Furthermore, the second composition has high sensitivity and, when used as an underlayer film, has excellent adhesion to a resist film, so that excellent resist patterns can be formed by using the second composition. Therefore, the second composition is suitable for use as a material for forming lithography films.

[0099] [Compound] The compound contained in the second lithography film-forming composition is a compound represented by formula (4) and / or a compound represented by formula (5).

[0100] [ka]

[0101] In formula (4), Each A independently represents an aromatic group having 6 to 10 carbon atoms; each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group; R 1 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Each Rx1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; Ry1's each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; m represents an integer of 0 to 4; n represents an integer of 0 to 4;

[0102] [ka]

[0103] In formula (5), Each A independently represents an aromatic group having 6 to 10 carbon atoms; each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group; R 2 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Each Rx2 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; Ry2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; m represents an integer of 0 to 4; n represents an integer of 0 to 4;

[0104] Compound (4) and compound (5) are preferably compounds represented by formula (6) and formula (7), respectively, because they can simultaneously satisfy high levels of solubility in organic solvents, storage stability and thin film formability, heat resistance, etching resistance, sensitivity, and resist pattern formability in a well-balanced manner as film-forming materials for lithography.

[0105] [ka]

[0106] In formula (6), P, R 1 , Rx1, Ry1, m, and n have the same meanings as in formula (4).

[0107] [ka]

[0108] In formula (7), P, R 2 , Rx2, Ry2, m, and n have the same meanings as in formula (5).

[0109] Each A independently represents an aromatic group having 6 to 10 carbon atoms, and is preferably a phenyl group or a naphthyl group, more preferably a phenyl group, since excellent etching resistance can be obtained.

[0110] Each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group, and is preferably a hydrogen atom, a crosslinkable group, or a dissociable group, more preferably a hydrogen atom, because these can favorably suppress thin film formability and film deterioration during high-temperature baking.

[0111] The alkyl group having 1 to 30 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, a tert-butyl group, a cyclohexyl group, and an adamantyl group.

[0112] Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group. The aryl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms.

[0113] Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, an allyl group, a 4-pentenyl group, an isopropenyl group, an isopentenyl group, a 2-heptenyl group, a 2-octenyl group, and a 2-nonenyl group.

[0114] Examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group and a propargyl group.

[0115] In this embodiment, the term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. Examples of such crosslinkable groups include alkoxy groups having 1 to 20 carbon atoms, groups having an allyl group, groups having a (meth)acryloyl group, groups having an epoxy(meth)acryloyl group, groups having a hydroxyl group, groups having a urethane(meth)acryloyl group, groups having a glycidyl group, groups having a vinyl-containing phenylmethyl group, groups having various alkynyl groups, groups having a carbon-carbon double bond, groups having a carbon-carbon triple bond, and groups containing these groups, and the like, and examples of such crosslinkable groups include groups that crosslink in the presence or absence of a catalyst. As the "group containing these groups", for example, an alkoxy group represented by -ORx (Rx is a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a hydroxyl group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, a group having a vinyl-containing phenylmethyl group, a group having various alkynyl groups, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, or a group containing these groups) is preferred. In this embodiment, when the functional groups (excluding crosslinkable groups) described above as constituting the compound overlap with crosslinkable groups, those that are not crosslinkable are treated as corresponding to the respective functional groups based on the presence or absence of crosslinkability, and those that are crosslinkable are treated as corresponding to the crosslinkable groups.

[0116] Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexanoxy group, and a 2-methylpropoxy group.

[0117] Examples of the group having an allyl group include groups represented by formulae (X-1a) and (X-1b).

[0118] [ka]

[0119] In formula (X-1b), n X1 is an integer from 1 to 5.

[0120] Examples of the group having a (meth)acryloyl group include groups represented by formulae (X-2a) to (X-2c).

[0121] [ka]

[0122] In formula (X-2c), n X2 is an integer of 1 to 5, and in formulas (X-2a) to (X-2c), R X is a hydrogen atom or a methyl group.

[0123] An example of a group having an epoxy(meth)acryloyl group is a group represented by the following formula (X-3): The epoxy(meth)acryloyl group refers to a group generated by reaction of an epoxy(meth)acrylate with a hydroxyl group.

[0124] [ka]

[0125] In formula (X-3), n x3 is an integer of 0 to 5, and is preferably 0 because excellent heat resistance and etching resistance can be obtained. X is a hydrogen atom or a methyl group, and a methyl group is preferred because excellent curability can be obtained.

[0126] Examples of the group having a urethane (meth)acryloyl group include a group represented by formula (X-4).

[0127] [ka]

[0128] In formula (X-4), n x4is an integer of 0 to 5, and is preferably 0 because excellent heat resistance and etching resistance can be obtained. s is an integer of 0 to 3, and is preferably 0 because excellent heat resistance and etching resistance can be obtained. R X is a hydrogen atom or a methyl group, and a methyl group is preferred because excellent curability can be obtained.

[0129] Examples of the group having a hydroxyl group include groups represented by the following formulae (X-5a) to (X-5e).

[0130] [ka]

[0131] In formulas (X-5b) and (X-5e), n x5 is an integer of 1 to 5, and is preferably 1 because excellent heat resistance and etching resistance can be obtained.

[0132] Examples of the group having a glycidyl group include groups represented by formulae (X-6a) to (X-6c).

[0133] [ka]

[0134] In formula (X-6b), n x6 is an integer from 1 to 5.

[0135] Examples of the group having a vinyl-containing phenylmethyl group include groups represented by formulae (X-7a) and (X-7b).

[0136] [ka]

[0137] In formula (X-7b), n x7 is an integer of 1 to 5, and is preferably 1 because excellent heat resistance and etching resistance can be obtained.

[0138] Examples of groups having various alkynyl groups include groups represented by the following formulae (X-8a) to (X-8h).

[0139] [ka]

[0140] In formulas (X-8b), (X-8d), (X-8f) and (X-8h), n x8 is an integer from 1 to 5.

[0141] Examples of the carbon-carbon double bond-containing group include a (meth)acryloyl group, a substituted or unsubstituted vinylphenyl group, and a group represented by formula (X-9). Examples of the carbon-carbon triple bond-containing group include a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, and groups represented by formulae (X-10a) and (X-10b).

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] In formula (X-9), R X9A , R X9B and R X9C are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X9D , R X9E and R X9F are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0146] In this embodiment, the term "dissociable group" refers to a group that dissociates in the presence or absence of a catalyst. Among dissociable groups, an acid-dissociable group refers to a group that is cleaved in the presence of an acid and changes into an alkali-soluble group or the like. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. Among these, from the viewpoint of easy availability of an introduction reagent, the phenolic hydroxyl group and the carboxyl group are preferred, and the phenolic hydroxyl group is more preferred. The acid-dissociable group preferably has the property of undergoing a chain cleavage reaction in the presence of an acid, in order to enable highly sensitive and high-resolution pattern formation. The acid-dissociable group can be appropriately selected from those proposed for hydroxystyrene resins and (meth)acrylic acid resins used in chemically amplified resist compositions for KrF and ArF. Examples of the acid-dissociable group include those described in WO 2016 / 158168. Examples of the acid-dissociable group include 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, silyl groups, acyl groups, 1-substituted alkoxymethyl groups, cyclic ether groups, alkoxycarbonyl groups (e.g., -C(O)OC(CH)), and alkoxycarbonylalkyl groups (e.g., -(CH) n C(O)OC(CH3)3 where n = 1 to 4. In the present embodiment, when the functional groups (excluding dissociative groups) described above as constituting the compound overlap with dissociative groups, those that are not dissociative are treated as corresponding to the functional groups, and those that are dissociative are treated as corresponding to the dissociative groups, based on whether or not they are dissociative.

[0147] Examples of substituents that can be substituted on the dissociative group include halogen atoms, alkyl groups, aryl groups, aralkyl groups, alkynyl groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkyloyloxy groups, aryloyloxy groups, cyano groups, and nitro groups. These groups may contain heteroatoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The alkyl group can be as described above, and examples thereof include alkyl groups having 1 to 10 carbon atoms such as a methyl group, a tert-butyl group, a cyclohexyl group, and an adamantyl group. The aryl group can be selected from the above, but is preferably an aryl group having 6 to 20 carbon atoms. The aryl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the aralkyl group include a benzyl group and a phenethyl group, etc. The aralkyl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms. The alkynyl group can be as described above. Examples of the acyl group include aliphatic acyl groups having 1 to 6 carbon atoms, such as a formyl group and an acetyl group, and aromatic acyl groups, such as a benzoyl group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 5 carbon atoms, such as a methoxycarbonyl group. An example of the alkyloyloxy group is an acetoxy group. An example of the aryloyloxy group is a benzoyloxy group.

[0148] Examples of heteroatoms include oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, and phosphorus atoms. Heteroatoms may replace carbon atoms in each group. The number of carbon atoms in each group described in this embodiment is the total number of carbon atoms including the substituent, if any.

[0149] R1 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and among these, an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms is preferred, and a phenyl group is more preferred. Examples of such groups include a phenyl group, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

[0150] Rx1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom. Among these, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred. Examples of such groups include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. m represents an integer of 0 to 4.

[0151] Ry1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom. Among these, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred. Examples of such groups include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. n represents an integer of 0 to 4.

[0152] R 2 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and among these, an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. Examples of such groups include a phenyl group, a naphthyl group, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

[0153] Rx2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a halogen atom, and among these, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred. Examples of such groups include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. m represents an integer of 0 to 4.

[0154] Ry2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a halogen atom, and among these, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred. Examples of such groups include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. n represents an integer of 0 to 4.

[0155] [Method for producing compounds] The method for producing compound (4) is not particularly limited, but for example, it can be produced from a phenol represented by formula (4-1) by a method known as a dehydration reaction.

[0156] [ka]

[0157] In formula (4-1), A, R 1 , Rx1, Ry1, m, and n are defined as in formula (4).

[0158] The phenols represented by formula (4-1) can be obtained by a known method of dehydration reaction between a phenolphthalein derivative represented by formula (4-2) and an amine derivative or an aniline derivative. For details of such dehydration reaction, see, for example, JP-A-2005-290378. Alternatively, they may be synthesized by other known methods.

[0159] [ka]

[0160] In formula (4-2), A, R 1 , Rx1, Ry1, m, and n are defined as in formula (4).

[0161] Examples of the amine derivatives include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, and cyclohexylamine.

[0162] Examples of aniline derivatives include aniline, o-methylaniline, m-methylaniline, p-methylaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, o-chloromethylaniline, m-chloromethylaniline, p-chloromethylaniline, o-trifluoromethylaniline, m-trifluoromethylaniline, p-trifluoromethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-carbomethoxyaniline, m-carbomethoxyaniline, p-carbomethoxyaniline, and o-acetamidoaniline. Acetoxyaniline, m-acetoxyaniline, p-acetoxyaniline, 1-naphthylamine, 2-naphthylamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-3-chlorophenol, 1-amino-2-naphthol, 2-amino-1-naphthol, 3-amino-2-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol ethanol, 5-amino-2-naphthol, 6-amino-1-naphthol, 8-amino-2-naphthol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 3-amino-p-cresol, 4-amino-m-cresol, 4-amino-o-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 4-amino-3,5-xylenol, and 3-hydroxy-4-methoxyaniline.

[0163] The compound (5) can be produced, for example, from a phenol represented by formula (5-1) by a method known as a dehydration reaction.

[0164] [ka]

[0165] In formula (5-1), A, R 2 , Rx2, Ry2, m, and n are defined as in formula (5).

[0166] The phenol represented by formula (5-1) can be produced by any known method, and is not particularly limited thereto. For example, it can be synthesized from indoline-2,3-dione represented by formula (5-2) and a phenol. For such a synthesis method, see, for example, JP 2002-179649 A.

[0167] [ka]

[0168] In formula (5-2), R 2 , Rx 2 is defined as in equation (5).

[0169] In the method for producing a phenol represented by formula (5-1), examples of the phenol to be reacted with indoline-2,3-dione represented by formula (5-2) include phenol, o-cresol, m-cresol, p-cresol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, p-tert-butylphenol, p-nonylphenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, and 3,5-xylenol, and resorcinol.

[0170] The compound represented by formula (5-2) can be produced by a known method.

[0171] 〔resin〕 The second composition for forming a lithography film may contain a resin obtained by polymerizing one or more of the compounds (4) to (7) as monomers. The resin may be a homopolymer made of one type of monomer, or a copolymer made by appropriately combining two or more types of monomers. The copolymer may be a block copolymer or a random copolymer. The resin may be an oligomer or a polymer. The resin of this embodiment is preferably a resin obtained by reacting one or more of the compounds (4) to (7) as monomers with a crosslinkable monomer. Such a resin may be an oligomerized resin or a polymer. An example of such a resin is a resin represented by formula (8) (hereinafter also referred to as "resin (8)"). When the second composition is used as a material for forming an underlayer film for lithography, it preferably contains a resin represented by formula (8).

[0172] [ka]

[0173] In formula (8), B is at least one selected from a structural unit derived from a compound represented by formula (4), a structural unit derived from a compound represented by formula (5), a structural unit derived from a compound represented by formula (6), and a structural unit derived from a compound represented by formula (7). When a plurality of these structural units are present, they may be in a block or random form. The resin is preferably obtained by reacting any one selected from a structural unit derived from a compound represented by formula (4), a structural unit derived from a compound represented by formula (5), a structural unit derived from a compound represented by formula (6), and a structural unit derived from a compound represented by formula (7) with a crosslinkable monomer.

[0174] L is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, or an arylene group having 1 to 20 carbon atoms which may have a substituent. When a plurality of B's ​​and / or L's are present, they are independent of each other. Unless otherwise defined, the term "substituent" refers to a functional group in which one or more hydrogen atoms have been replaced with an atom other than a hydrogen atom or a functional substituent. The number of substituents is not particularly limited and may be one or more.

[0175] Examples of the linear or branched alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a 2,2-dimethylpropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, an undecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a neopentylene group, a dimethylbutylene group, a methylene group, a methyl ... Examples of the alkylene group include methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene groups.

[0176] Examples of the arylene group having 1 to 20 carbon atoms include phenylene groups such as a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group; naphthalenediyl groups such as a 1,4-naphthalenediyl group, a 1,5-naphthalenediyl group, a 2,6-naphthalenediyl group, and a 2,7-naphthalenediyl group; anthracenediyl groups such as a 1,4-anthracenediyl group, a 1,5-anthracenediyl group, a 2,6-anthracenediyl group, and a 9,10-anthracenediyl group; phenanthrenediyl groups such as a 2,7-phenanthrenediyl group; dihydrophenanthrenediyl groups such as a 9,10-dihydrophenanthrene-2,7-diyl group; and 1,7-naphthacenediyl. naphthacenediyl groups such as a 2,8-naphthacenediyl group, and a 5,12-naphthacenediyl group; fluorenediyl groups such as a 2,7-fluorenediyl group and a 3,6-fluorenediyl group; pyrenediyl groups such as a 1,6-pyrenediyl group, a 1,8-pyrenediyl group, a 2,7-pyrenediyl group, and a 4,9-pyrenediyl group; perylenediyl groups such as a 3,8-perylenediyl group, a 3,9-perylenediyl group, and a 3,10-perylenediyl group; and spirofluorenediyl groups such as a 9,9'-spirofluorene-2,7-diyl group, a 9,9'-spirofluorene-3,6-diyl group, and a 9,9'-spirofluorene-2,2'-diyl group.

[0177] The crosslinkable compound may be any compound capable of oligomerizing or polymerizing Compounds (4) to (7), and examples thereof include aldehydes, ketones, carboxylic acids, halogen-containing compounds such as acid halides and alkyl halides, amino compounds, imino compounds, isocyanate compounds, and unsaturated hydrocarbon group-containing compounds. These crosslinkable compounds may be used alone or in combination of two or more.

[0178] These crosslinkable compounds can suitably crosslink the aromatic groups of compounds (4) to (7) in the presence of a catalyst, thereby forming a more stable film. Therefore, by using a resin crosslinked with these compounds, it is possible to obtain a composition that is useful as a film-forming material for lithography, which has high solubility in organic solvents, excellent storage stability and thin-film formability, high etching resistance, excellent heat resistance, high sensitivity, and excellent resist pattern formability, and which satisfies these physical properties in a well-balanced manner at a high level.

[0179] As the resin (8), for example, a novolak resin obtained by a condensation reaction between the compounds (4) to (7) and aldehydes or ketones, which are crosslinkable compounds, is preferred because it has excellent reactivity.

[0180] The aldehydes can be used alone or in combination of two or more thereof. In addition to the aldehydes, one or more ketones can also be used in combination. As the aldehydes, from the viewpoint of being able to improve etching resistance and to exhibit high heat resistance, formaldehyde, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural are preferred. From the viewpoints of low oxidation resistance, high reactivity, improved etching resistance, and higher heat resistance, formaldehyde, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural are more preferred, and formaldehyde is even more preferred. The amount of aldehydes used is not particularly limited, but is preferably 0.2 to 10 mol, more preferably 0.5 to 8 mol, per mol of the total amount of Compounds (4) to (7).

[0181] As the ketones, from the viewpoint of being able to improve etching resistance and to exhibit high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylbenzene, In view of being able to further improve etching resistance and exhibit higher heat resistance, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl are more preferred. The amount of ketones used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per mole of the total amount of Compounds (4) to (7).

[0182] Examples of carboxylic acids include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

[0183] Examples of halogen-containing compounds include compounds containing halogenated alkyl groups and halogenated aryl groups. Examples of halogenated alkyl groups include trifluoromethyl groups, 1,1,1-trifluoroethyl groups, 1,1,1-trichloroethyl groups, and nonafluorobutyl groups. Examples of halogenated aryl groups include fluorophenyl groups, chlorophenyl groups, and 1,2,3,4,5-pentafluorophenyl groups.

[0184] Examples of amino compounds include those described in International Publication No. 2018-016614.

[0185] Examples of imino compounds include 2,2'-iminodiethanol, ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine.

[0186] Examples of the isocyanate compound include those described in International Publication No. 2018-016614.

[0187] Examples of the unsaturated hydrocarbon group-containing compound include a compound having an allyl group and a compound having an alkynyl group.

[0188] Alternatively, for example, aromatic rings of only one or more of compounds (4) to (7) may be polymerized together by one-electron oxidation polymerization in the presence of an oxidizing agent, and in this case, L in formula (8) represents a single bond. Examples of oxidizing agents that can be used include metal salts or metal complexes containing copper, manganese, iron, cobalt, ruthenium, chromium, or palladium, peroxides such as hydrogen peroxide and perchloric acids, and organic peroxides. Among these, metal salts or metal complexes containing copper, manganese, iron, or cobalt are preferred. Metals such as copper, manganese, iron, cobalt, ruthenium, chromium, and palladium can also be used as oxidizing agents by reducing them in the reaction system. These are included in metal salts. The oxidizing agents may be used alone or in a suitable mixture of two or more.

[0189] The resin of this embodiment may be a homopolymer of at least one selected from Compounds (4) to (7), a resin crosslinked with a crosslinkable compound, or a copolymer obtained by polymerizing such a resin with other phenols. Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, propylphenol, pyrogallol, and thymol.

[0190] The resin of this embodiment may be copolymerized with a polymerizable monomer other than the above-mentioned other phenols. Examples of the copolymerizable monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinylnorbornaene, pinene, and limonene. The resin of this embodiment may be a two or more component (e.g., two to four component) copolymer of a resin crosslinked with Compounds (4) to (7) or a compound having crosslinking activity and a phenol; a two or more component (e.g., two to four component) copolymer of a resin crosslinked with Compounds (4) to (7) or a compound having crosslinking activity and a copolymerizing monomer; or a three or more component (e.g., three to four component) copolymer of a resin crosslinked with Compounds (4) to (7) or a compound having crosslinking activity, a phenol, and a copolymerizing monomer.

[0191] The mass average molecular weight (Mw) of the resin of this embodiment, calculated as polystyrene by GPC measurement, is preferably 300 to 100,000, more preferably 500 to 30,000, and even more preferably 750 to 20,000. From the viewpoints of increasing crosslinking efficiency and suppressing volatile components during baking, the resin of this embodiment preferably has a polydispersity (mass average molecular weight Mw / number average molecular weight Mn) in the range of 1 to 7.

[0192] Compounds (4) to (7) and resins preferably have high solubility in solvents, from the viewpoint of facilitating the application of wet processes. For example, when propylene glycol monomethyl ether (hereinafter also referred to as "PGME"), propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA"), and / or cyclohexanone (hereinafter also referred to as "CHN") are used as the solvent, compounds (4) to (7) and resins preferably have a solubility in the solvent of 5% by mass or more. Here, the solubility in PGME and / or PGMEA is defined as "total amount of compounds (4) to (7) and resin / (total amount of compounds (4) to (7) and resin + total amount of solvent) × 100 (% by mass)." For example, a total amount of 5 g of compounds (4) to (7) and a resin is evaluated as being highly soluble in 95 g of PGMEA when the solubility of compounds (4) to (7) and the resin in PGMEA is "5% by mass or more," and is evaluated as not being highly soluble when the solubility is "less than 5% by mass."

[0193] Examples of compounds (4) to (7) and resins include compounds represented by the following formulae: In addition, for resins, partial structures are shown.

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [Method for producing resin] The resin of this embodiment can be obtained by polymerizing one or more of the compounds (4) to (7) as monomers using a known method, for example, by electrochemical oxidation polymerization in the presence of an oxidizing agent. In addition, in the resin (8) of this embodiment, a known method can also be used for the crosslinking method using a crosslinkable compound. For example, the resin can be obtained by using one or more of the compounds (4) to (7) as monomers and subjecting these monomers to a condensation reaction with a crosslinkable compound in the presence of an acid catalyst or a base catalyst.

[0200] A catalyst can also be used in the method of polymerizing one or more of Compounds (4) to (7) as a monomer, and in the condensation reaction using a crosslinkable compound. The acid catalyst or base catalyst used here can be appropriately selected from known catalysts. Examples of acid catalysts include organic acids and solid acids. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. Examples of basic catalysts include metal alkoxides (alkali metal or alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide); metal hydroxides (alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide); alkali metal or alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; amines (e.g., tertiary amines (trialkylamines such as triethylamine, aromatic tertiary amines such as N,N-dimethylaniline, and heterocyclic tertiary amines such as 1-methylimidazole)); and organic bases such as metal carboxylates (alkali metal or alkaline earth metal acetates such as sodium acetate and calcium acetate). These catalysts may be used alone or in combination. From the viewpoint of production, organic acids and solid acids are preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production, such as ease of availability and handling. The amount of acid catalyst used can be appropriately set depending on the raw materials and catalyst used, as well as the reaction conditions, and is preferably 0.01 to 100 parts by mass, for example, per 100 parts by mass of the reaction raw materials.

[0201] In the present embodiment, in the case of a copolymerization reaction between a compound having a non-conjugated double bond, such as indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, or limonene, and a crosslinkable compound, the compound does not have to be an aldehyde or a ketone.

[0202] In the method of polymerizing one or more of Compounds (4) to (7) as monomers, and in the condensation reaction using a crosslinkable compound, a reaction solvent can also be used. The reaction solvent for this polycondensation can be appropriately selected from known solvents, and examples thereof include water, methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol, tetrahydrofuran, dioxane, xylenes such as ortho-xylene, and mixed solvents thereof. These solvents can be used alone or in combination of two or more.

[0203] The amount of solvent used can be appropriately set depending on the types of raw materials and catalysts used, as well as the reaction conditions, and is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. Furthermore, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw materials and is typically in the range of 10 to 200°C, for example. Examples of reaction methods include a method in which Compounds (4) to (7) and an oxidizing agent are charged all at once, and a method in which these compounds and an oxidizing agent are charged sequentially. Examples of reaction methods include a method in which Compounds (4) to (7) and a catalyst are charged all at once, and a method in which these compounds and a catalyst are charged sequentially. Examples of reaction methods include a method in which Compounds (4) to (7), a crosslinkable compound such as an aldehyde or a ketone, and a catalyst are charged all at once, and a method in which Compounds (4) to (7), a crosslinkable compound such as an aldehyde or a ketone, are added dropwise sequentially in the presence of a catalyst.

[0204] After the polycondensation reaction is completed, the obtained resin can be isolated by a conventional method. For example, in order to remove unreacted raw materials, catalysts, and the like present in the system, the temperature of the reaction vessel is increased to 130 to 230°C, and volatile matters are removed at about 1 to 50 mmHg. This is a common method to obtain the target product (for example, a novolakized resin).

[0205] [solvent] The composition of the present embodiment may further contain a solvent. The solvent is not particularly limited as long as it can dissolve the compounds (1), (3) to (7) of the present embodiment and the resin, and various organic solvents are suitably used.

[0206] The solvent is not particularly limited, but examples thereof include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); cellosolve-based solvents such as PGME (propylene glycol monomethyl ether) and PGMEA (propylene glycol monomethyl ether acetate); ester-based solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; alcohol-based solvents such as methanol, ethanol, isopropanol, and 1-ethoxy-2-propanol; and aromatic hydrocarbons such as toluene, xylene, and anisole. These solvents may be used alone or in combination of two or more.

[0207] Among the above solvents, from the viewpoint of safety, when used in the first composition, it is preferable to use one or more solvents selected from the group consisting of cyclohexanone, PGME, PGMEA, ethyl lactate, methyl hydroxyisobutyrate, and anisole. When used in the second composition, it is preferable to use a safe solvent, more preferably PGME, PGME, CHN, CPN, 2-heptanone, anisole, methyl hydroxyisobutyrate, butyl acetate, ethyl propionate, and ethyl lactate, and even more preferably PGMEA, PGME, and CHN. These solvents may be used alone or in combination of two or more. Note that the solvents described below in the composition for forming a resist film may also be used as the solvent.

[0208] In the composition of the present embodiment, the amount of solid components is not particularly limited, but is preferably 1 to 80 mass %, more preferably 1 to 50 mass %, even more preferably 2 to 40 mass %, and even more preferably 2 to 10 mass % and 90 to 98 mass % of the solvent, relative to 100 mass % of the total mass of the solid components and the solvent.

[0209] In the composition of the present embodiment, the amount of solvent is not particularly limited, but is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, even more preferably 60 to 98% by mass, and even more preferably 90 to 98% by mass, relative to 100% by mass of the total mass of the solid components and solvent. In this specification, "solid components" refers to components other than the solvent.

[0210] The content of the solvent is not particularly limited, but from the viewpoints of solubility and film formation, it is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and even more preferably 200 to 1,000 parts by mass, relative to 100 parts by mass of the total mass of Compound (1) and Compound (3) in the first composition, or 100 parts by mass of the total mass of Compounds (4) to (7) and the resin in the second composition.

[0211] [Crosslinking agent] The composition of the present embodiment may further contain a crosslinking agent from the viewpoint of suppressing intermixing, etc. The crosslinking agent is not particularly limited, but for example, those described in WO 2013 / 024778, WO 2013 / 024779, and WO 2018 / 016614 can be used.

[0212] The crosslinking agent is not particularly limited, but examples thereof include phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds. These crosslinking agents may be used alone or in combination of two or more. In the first composition, among these, one or more selected from the group consisting of benzoxazine compounds, epoxy compounds, and cyanate compounds are preferred, with benzoxazine compounds being more preferred from the viewpoint of improving etching resistance. In the second composition, among these, melamine compounds, urea compounds, benzoxazine compounds, epoxy compounds, and cyanate compounds are preferred, with melamine compounds and urea compounds being more preferred from the viewpoint of good reactivity. Examples of melamine compounds include a compound represented by formula (a) (Nicalac MW-100LM (trade name), manufactured by Sanwa Chemical Co., Ltd.) and a compound represented by formula (b) (Nicalac MX270 (trade name), manufactured by Sanwa Chemical Co., Ltd.).

[0213] [ka] In this embodiment, the content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total mass of Compounds (1) and (3) in the first composition, or 100 parts by mass of the total mass of Compounds (4) to (7) and the resin in the second composition. By keeping the content of the crosslinking agent within the above range, the occurrence of mixing with the resist film tends to be suppressed, and the antireflection effect and film formability after crosslinking tend to be improved.

[0214] [Crosslinking accelerator] The composition of this embodiment may further contain a crosslinking accelerator to accelerate the crosslinking reaction (curing reaction) as needed. Examples of the crosslinking accelerator include radical polymerization initiators. Examples of the crosslinking accelerator include the compounds disclosed in WO 2013 / 024778, WO 2013 / 024779, and WO 2017 / 033943.

[0215] The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or a thermal polymerization initiator that initiates radical polymerization by heat. The radical polymerization initiator is not particularly limited, but examples thereof include ketone-based photopolymerization initiators, organic peroxide-based polymerization initiators, and azo-based polymerization initiators.

[0216] Such a radical polymerization initiator is not particularly limited, but for example, those described in WO 2018 / 016614 can be used.

[0217] These radical polymerization initiators may be used alone or in combination of two or more.

[0218] The content of the radical polymerization initiator in this embodiment is not particularly limited, but is preferably 0.05 to 25 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total mass of Compound (1) and Compound (3) in the first composition, or 100 parts by mass of the total mass of Compounds (4) to (7) and the resin in the second composition. When the content of the radical polymerization initiator is 0.05 parts by mass or more, insufficient curing tends to be prevented, while when the content of the radical polymerization initiator is 25 parts by mass or less, deterioration of long-term storage stability at room temperature tends to be prevented.

[0219] [Acid generator] The composition of the present embodiment may further contain an acid generator from the viewpoint of further promoting the crosslinking reaction by heat, etc. Known acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either can be used. The acid generator is not particularly limited, but for example, those described in WO 2013 / 024778, WO 2013 / 024779, and WO 2017 / 033943 can be used.

[0220] The acid generator is preferably an acid generator having an aromatic ring, more preferably an acid generator having a sulfonate ion with an aryl group, and even more preferably di-tert-butyldiphenyliodonium nonafluoromethanesulfonate, diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate. The use of an acid generator can reduce line edge roughness. These acid generators may be used alone or in combination of two or more.

[0221] The content of the acid generator in the composition of this embodiment is not particularly limited, but is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 40 parts by mass, relative to 100 parts by mass of the total mass of Compound (1) and Compound (3) in the first composition, or 100 parts by mass of the total mass of Compounds (4) to (7) and the resin in the second composition. When the content of the acid generator is within the above range, the crosslinking reaction tends to be enhanced, and the occurrence of mixing with the resist film tends to be suppressed.

[0222] [Basic compounds] The composition of the present embodiment may further contain a basic compound from the viewpoint of improving storage stability, etc. The basic compound serves to inhibit the progress of the crosslinking reaction caused by a small amount of acid generated from the acid generator, i.e., serves as a quencher for the acid. Examples of such basic compounds include, but are not limited to, those described in International Publication Nos. 2013 / 024778, 2013 / 024779, and 2017 / 033943. These basic compounds may be used singly or in combination of two or more.

[0223] The content of the basic compound in the composition of this embodiment is not particularly limited, but is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total mass of Compounds (1) and (3) in the first composition, or 100 parts by mass of the total mass of Compounds (4) to (7) and the resin in the second composition. When the content of the basic compound is within the above range, storage stability tends to be improved without excessively impairing the crosslinking reaction.

[0224] [Acid diffusion inhibitor] The lithographic film-forming composition of this embodiment may contain an acid diffusion controller to control the diffusion of the acid generated from the acid generator upon irradiation in the resist film and prevent undesirable chemical reactions in unexposed areas. The use of an acid diffusion controller tends to improve the storage stability of the composition. Furthermore, the use of an acid diffusion controller tends to improve the resolution of a film formed using the composition, and also tends to suppress changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, thereby resulting in excellent process stability. Examples of acid diffusion controllers include nitrogen-containing basic compounds such as tributylamine and trioctylamine, basic sulfonium compounds, and radiation-decomposable basic compounds such as basic iodonium compounds.

[0225] Examples of the acid diffusion controller include the compounds disclosed in WO 2013 / 024778, WO 2013 / 024779, and WO 2017 / 033943. These acid diffusion controllers may be used alone or in combination of two or more.

[0226] The content of the acid diffusion controller in the composition is, for example, preferably 0.001 to 49 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the total mass of Compound (1) and Compound (3) in the first composition, or 100 parts by mass of the total mass of Compounds (4) to (7) and the resin in the second composition. When the amount of the acid diffusion controller is within the above range, deterioration of resolution, pattern shape, dimensional fidelity, and the like tends to be prevented. Furthermore, deterioration of the shape of the upper layer of the pattern can be suppressed even if the storage time between electron beam irradiation and post-irradiation heating is long. Furthermore, when the amount is 10 parts by mass or less, deterioration of sensitivity, developability of unexposed areas, and the like tends to be prevented. The use of such an acid diffusion controller tends to improve the storage stability of the composition, improve resolution, and produce a good resist pattern.

[0227] [Additives] The composition of this embodiment may further contain additives other than the solvent, crosslinking agent, crosslinking accelerator, acid generator, basic compound, and acid diffusion inhibitor described above, for the purpose of imparting heat or light curability or controlling absorbance. Examples of such additives include, but are not limited to, naphthol resins, xylene resins, naphthol-modified resins, and phenol-modified naphthalene resins; resins containing heterocycles with heteroatoms, such as polyhydroxystyrene, dicyclopentadiene resins, (meth)acrylates, dimethacrylates, trimethacrylates, tetramethacrylates, vinylnaphthalene, and polyacenaphthylene; biphenyl rings, such as phenanthrenequinone and fluorene; thiophenes; and indene; resins or compounds containing alicyclic structures, such as rosin resins, cyclodextrins, adamantane (poly)ols, tricyclodecane (poly)ols, and derivatives thereof. The composition of this embodiment may also contain known additives used in lithography film formation. Known additives include, but are not limited to, heat and / or light curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, light curing resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.

[0228] [Resist film-forming composition] The composition of the present embodiment is preferably used for forming a resist film. That is, the resist film of the present embodiment contains the composition of the present embodiment. A film formed by applying the composition of the present embodiment can also be used to form a resist pattern, if necessary.

[0229] The composition of the present embodiment can be used as a film-forming composition for lithography intended for use in chemically amplified resists (hereinafter also referred to as a "resist film-forming composition"). Components that may be contained in the resist film-forming composition will be described below in particular.

[0230] The resist film-forming composition of this embodiment preferably contains a solvent. The solvent is not particularly limited, but examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as PGMEA, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as PGME and propylene glycol monoethyl ether; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; methyl acetate, ethyl acetate, and n-propyl acetate. aliphatic carboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, and 3-methoxy-3-methylbutyric acid; Examples of suitable solvents include other esters such as butyl, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (hereinafter also referred to as "CPN"), and cyclohexanone (hereinafter also referred to as "CHN"); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-lactone. These solvents may be used singly or in combination of two or more.

[0231] The solvent used in the present embodiment is preferably a safe solvent, more preferably one or more selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and even more preferably one or more selected from PGMEA, PGME, and CHN.

[0232] In the composition for forming a resist film of the present embodiment, the amount of the solid components is not particularly limited, but is preferably 1 to 80 mass %, more preferably 1 to 50 mass %, even more preferably 2 to 40 mass %, and even more preferably 2 to 10 mass % and 90 to 98 mass % of the solvent, relative to 100 mass % of the total mass of the solid components and the solvent. In the composition for forming a resist film of the present embodiment, the amount of the solvent is not particularly limited, but is preferably 20 to 99 mass %, more preferably 50 to 99 mass %, even more preferably 60 to 98 mass %, and even more preferably 90 to 98 mass %, relative to 100 mass % of the total mass of the solid components and the solvent.

[0233] The composition for forming a resist film of the present embodiment may further contain, as a solid component other than the compound (1), compound (3), compounds (4) to (7) and resin of the present embodiment, one or more selected from the group consisting of an acid generator, an acid crosslinker, an acid diffusion controller, and other components.

[0234] Here, the acid generator, acid crosslinker, acid diffusion controller, and other components can be known and are not particularly limited, but for example, those described in WO 2013 / 024778 are preferred.

[0235] In the resist film-forming composition of this embodiment, the total mass of compound (1), compound (3), compounds (4) to (7), and resin used as the resist base material is not particularly limited, but is preferably 1 to 100% by mass, more preferably 50 to 99.4% by mass, even more preferably 55 to 90% by mass, even more preferably 60 to 80% by mass, and even more preferably 60 to 70% by mass, based on the total mass of the solid components. When the total mass of compound (1) and compound (3) in the first composition, or the total mass of compounds (4) to (7) and resin in the second composition, is within the above range, resolution tends to be further improved and line edge roughness (hereinafter also referred to as "LER") tends to be further reduced.

[0236] The resist film-forming composition of the present embodiment may further contain, as necessary, a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, an organic carboxylic acid or a phosphorus oxoacid or a derivative thereof, a heat curing catalyst, a photocuring catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a photocurable resin, a dye, a pigment, a thickener, a lubricant, an antifoaming agent, a leveling agent, an ultraviolet absorber, a surfactant such as a nonionic surfactant, a colorant, and various additives, provided that the object of the present invention is not impaired. These additives may be used alone or in combination of two or more.

[0237] In the composition for forming a resist film of this embodiment, the contents of the compound (1), compound (3), compounds (4) to (7), resin, acid generator, acid crosslinker, acid diffusion controller, and other components of this embodiment (compound (1) and compound (3), or compounds (4) to (7) and resin / acid generator / acid crosslinker / acid diffusion controller / other components) are, in mass % on a solid basis, Preferably 1-100 / 0-49 / 0-49 / 0-49 / 0-99, More preferably, 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49 / 0 to 49, More preferably, 55-90 / 1-40 / 0.5-40 / 0.01-10 / 0-5. Even more preferably, 60-80 / 3-30 / 1-30 / 0.01-5 / 0-1; Even more preferably, 60-70 / 10-25 / 2-20 / 0.01-3 / 0, is. The blending ratio of each component is selected from the respective ranges so that the total sum is 100% by mass. When the blending ratio of each component is within the above range, the performance such as sensitivity, resolution, and developability tends to be excellent.

[0238] The resist film-forming composition of this embodiment is usually prepared at the time of use by dissolving each component in a solvent to form a homogeneous solution, and then filtering the solution, if necessary, using a filter with a pore size of about 0.2 μm, for example.

[0239] The resist film-forming composition of this embodiment may contain other resins in addition to the resin of this embodiment, provided that the object of this embodiment is not impaired. Examples of other resins include, but are not limited to, novolac resins, polyvinylphenols, polyacrylic acids, epoxy resins, polyvinyl alcohols, styrene-maleic anhydride resins, and addition polymerization resins. The addition polymerization resin is not particularly limited, but examples thereof include polymers containing acrylic acid, vinyl alcohol, vinylphenol, or a maleimide compound as a monomer unit, and derivatives thereof. The content of the other resin is not particularly limited and is adjusted appropriately depending on the types of compound (1), compound (3), compounds (4) to (7) and resins of the present embodiment used. However, the content is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 0 part by mass, relative to 100 parts by mass of the total mass of compound (1) and compound (3) in the first composition, or 100 parts by mass of the total mass of compounds (4) to (7) and resins in the second composition.

[0240] The resist film-forming composition of this embodiment can be used to form an amorphous film by spin coating. Furthermore, the resist film-forming composition of this embodiment can be applied to general semiconductor manufacturing processes. Depending on the types of compound (1), compound (3), compounds (4) to (7), and resin, and the type of developer used, either a positive resist pattern or a negative resist pattern can be formed.

[0241] In the case of a positive resist pattern, the dissolution rate of an amorphous film formed by spin-coating the resist film-forming composition of this embodiment in a developer at 23°C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, the film tends to be insoluble in the developer and to be easily converted into a resist. Furthermore, when the dissolution rate is 0.0005 Å / sec or more, resolution may be improved. This is presumably because the change in solubility of compound (1), compound (3), compounds (4) to (7), and the resin of this embodiment before and after exposure increases the contrast at the interface between the exposed portion that dissolves in the developer and the unexposed portion that does not dissolve in the developer. Furthermore, the effect of reducing LER and defects is also observed.

[0242] In the case of a negative resist pattern, the dissolution rate of an amorphous film formed by spin-coating the resist film-forming composition of this embodiment in a developer at 23°C is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, the film is easily soluble in the developer and is suitable for use as a resist. Furthermore, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the micro-surface portions of the compound (1), compound (3), compounds (4) to (7), and resin of this embodiment dissolve, reducing LER. Furthermore, a defect reduction effect is also observed.

[0243] The dissolution rate can be determined by immersing an amorphous film in a developer at 23° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.

[0244] In the case of a positive resist pattern, the dissolution rate in a developer at 23°C of the portion of an amorphous film formed by spin-coating the resist film-forming composition of this embodiment, which has been exposed to radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, is preferably 10 Å / sec or more. A dissolution rate of 10 Å / sec or more means that the film is readily soluble in a developer and is suitable for use as a resist. Furthermore, a dissolution rate of 10 Å / sec or more may improve resolution. This is presumably due to the dissolution of the micro-surface regions of Compound (1), Compound (3), Compounds (4) to (7), and the resin of this embodiment, thereby reducing LER. Furthermore, a defect-reducing effect is also observed.

[0245] In the case of a negative resist pattern, the dissolution rate in a developer at 23°C of the portion of an amorphous film formed by spin-coating the resist film-forming composition of this embodiment, exposed to radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. A dissolution rate of 5 Å / sec or less tends to make the film insoluble in the developer, making it easier to form a resist. Furthermore, a dissolution rate of 0.0005 Å / sec or more may improve resolution. This is presumably due to the change in solubility of Compound (1), Compound (3), Compounds (4) to (7), and the resin of this embodiment before and after exposure, which increases the contrast at the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer. Furthermore, the effect of reducing LER and defects is also observed.

[0246] The compound (1), the compound (3), the compounds (4) to (7), and the resin contained in the composition for forming a resist film of the present embodiment are selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and are soluble in a solvent that exhibits the highest solubility for the compound (1), the compound (3), the compounds (4) to (7), and the resin at 23°C, preferably at 1% by mass or more, more preferably at 5% by mass or more, and even more preferably at 10% by mass or more. Compound (1), compound (3), compounds (4) to (7), and resin contained in the resist film-forming composition of this embodiment are soluble in a solvent selected from the group consisting of PGMEA, PGME, and CHN at 23° C., preferably at 20% by mass or more, and more preferably at 20% by mass or more relative to PGMEA at 23° C. By satisfying the above conditions, the composition can be easily used in the semiconductor manufacturing process in actual production.

[0247] The resist film-forming composition of this embodiment may contain other resins than those of this embodiment, provided that the purpose of this embodiment is not impaired. Examples of such other resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or derivatives thereof. The amount of these resins is adjusted appropriately depending on the types of compound (1), compound (3), compounds (4) to (7), and resins used. However, the amount of these resins is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass, per 100 parts by mass of the total mass of compound (1) and compound (3) in the first composition, or per 100 parts by mass of the total mass of compounds (4) to (7) and resins in the second composition.

[0248] [Permanent resist film] The composition of this embodiment is also preferably used to form a resist pattern as needed and then form a permanent resist film that remains in the final product. That is, the permanent resist film of this embodiment includes the composition of this embodiment. A film formed by applying the composition of this embodiment is suitable as a permanent resist film that remains in the final product after forming a resist pattern as needed. Specific examples of permanent films include, in the semiconductor device field, solder resist, packaging materials, underfill materials, package adhesive layers for circuit elements, and adhesive layers between integrated circuit elements and circuit boards; and in the flat panel display field, thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, and the like. In particular, a permanent resist film containing the composition of this embodiment has the excellent advantages of excellent heat resistance and moisture resistance, as well as low contamination by sublimation components. In particular, it serves as a material that combines high sensitivity, high heat resistance, and moisture absorption reliability, which are important for reducing image quality degradation due to contamination, especially in display materials.

[0249] When the composition of the present embodiment is used for forming a permanent resist film, in addition to a curing agent, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution promoters may be added as needed, and the resulting mixture may be dissolved in an organic solvent to form a composition for forming a permanent resist film.

[0250] [Composition for forming resist underlayer film] The composition of the present embodiment is also preferably a composition used for forming a resist underlayer film (hereinafter also referred to as a "composition for forming a resist underlayer film"). That is, the resist underlayer film of the present embodiment contains the composition of the present embodiment.

[0251] Any of the components described above as components that may be contained in the composition for forming a resist film can be similarly applied to the composition for forming a resist underlayer film of this embodiment.

[0252] [Method for forming resist pattern] The resist pattern forming method of this embodiment preferably includes a resist underlayer film forming step of forming a resist underlayer film on a substrate using the resist underlayer film forming composition of this embodiment, a photoresist film forming step of forming at least one photoresist film on the resist underlayer film, and a development step of irradiating predetermined regions of the photoresist film formed in the photoresist film forming step with radiation and developing the photoresist film to obtain a resist pattern. Such a resist pattern forming method can be used to form various patterns, and is preferably a method of forming an insulating film pattern. The method for forming a resist pattern of this embodiment also preferably includes a photoresist layer forming step of forming a photoresist layer on a substrate using the composition for forming a resist film of this embodiment, and a development step of irradiating predetermined regions of the photoresist layer with radiation and developing the photoresist layer to obtain a resist pattern. This method for forming a resist pattern can also be used to form various patterns, and is preferably a method for forming an insulating film pattern.

[0253] [Circuit pattern formation method] The method for forming a circuit pattern of this embodiment includes a resist underlayer film formation step of forming a resist underlayer film on a substrate using the resist underlayer film formation composition of this embodiment; an intermediate layer film formation step of forming an intermediate layer film on the resist underlayer film; a photoresist film formation step of forming at least one photoresist film on the intermediate layer film; a resist pattern formation step of obtaining a resist pattern by irradiating predetermined regions of the photoresist film with radiation and developing it; an intermediate layer film pattern formation step of etching the intermediate layer film using the resist pattern as a mask to obtain an intermediate layer film pattern; a resist underlayer film pattern formation step of etching the resist underlayer film using the intermediate layer film pattern as a mask to obtain a resist underlayer film pattern; and a substrate pattern formation step of etching the substrate using the resist underlayer film pattern as a mask to obtain a substrate pattern.

[0254] The photoresist film and resist underlayer film of this embodiment are formed from the film-forming composition for lithography of this embodiment. The formation method is not particularly limited, and known methods can be applied. For example, the film-forming composition for lithography of this embodiment is applied to a substrate by a known coating method, printing method, etc., such as spin coating or screen printing, and then the organic solvent is removed by volatilization, etc., to form the photoresist film and resist underlayer film.

[0255] When forming the resist underlayer film, it is preferable to bake it to prevent mixing with the resist toplayer film and promote the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450°C, more preferably 200 to 400°C. The baking time is also not particularly limited, but is preferably in the range of 10 to 300 seconds. The thickness of the resist underlayer film can be appropriately selected depending on the required performance, and is not particularly limited, but is preferably 30 to 20,000 nm, more preferably 50 to 15,000 nm.

[0256] After preparing the resist underlayer film, in the case of a two-layer process, it is preferable to prepare a silicon-containing resist film or a hydrocarbon monolayer resist on the resist underlayer film, and in the case of a three-layer process, it is preferable to prepare a silicon-containing intermediate layer on the resist underlayer film, and then prepare a silicon-free monolayer resist on the silicon-containing intermediate layer. In this case, known photoresist materials can be used to form this resist film.

[0257] From the viewpoint of etching resistance, silicon-containing resist materials for two-layer processes are preferably positive photoresist materials that use a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative as a base polymer, and further contain an organic solvent, an acid generator, and optionally a basic compound, etc. Here, known polymers used in this type of resist material can be used as the silicon atom-containing polymer.

[0258] A polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process. By providing the intermediate layer with the function of an anti-reflection coating, reflection tends to be effectively suppressed. For example, in a 193 nm exposure process, if a material containing many aromatic groups and having high substrate etching resistance is used as the resist underlayer, the k value tends to be high and the substrate reflection tends to be high. However, by suppressing reflection with the intermediate layer, the substrate reflection can be reduced to 0.5% or less. Examples of intermediate layers having such anti-reflection effects include, but are not limited to, acid- or heat-crosslinkable polysilsesquioxanes into which phenyl groups or light-absorbing groups having silicon-silicon bonds are introduced, and which are preferably used for 193 nm exposure.

[0259] Alternatively, an intermediate layer formed by a chemical vapor deposition (CVD) method can be used. Examples of intermediate layers produced by a CVD method that are highly effective as anti-reflection films include, but are not limited to, SiON films. Generally, forming an intermediate layer by a wet process such as spin coating or screen printing is more convenient and cost-effective than using a CVD method. The top layer resist in a three-layer process may be either a positive or negative resist, and the same resist as a commonly used single-layer resist can be used.

[0260] Furthermore, the resist underlayer film of this embodiment can also be used as an anti-reflection film for a normal single-layer resist or as an underlayer material for suppressing pattern collapse. The resist underlayer film has excellent etching resistance for underlayer processing, and therefore can also be expected to function as a hard mask for underlayer processing.

[0261] When forming a photoresist film using the film-forming composition for lithography of this embodiment, wet processes such as spin coating and screen printing are preferably used, as in the case of forming the resist underlayer film. After applying the resist material by spin coating or the like, pre-baking is typically performed, preferably at 80 to 180°C for 10 to 300 seconds. Thereafter, exposure, post-exposure baking (PEB), and development are performed according to conventional methods to obtain a resist pattern. The thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.

[0262] The exposure light may be appropriately selected depending on the photoresist material used, and generally includes high-energy rays with a wavelength of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, X-rays, etc.

[0263] The resist pattern formed by the above-described method is prevented from pattern collapse by the resist underlayer film, and therefore, by using the resist underlayer film of this embodiment, a finer pattern can be obtained and the exposure dose required to obtain the resist pattern can be reduced.

[0264] Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used to etch the resist underlayer film in the two-layer process. For gas etching, oxygen gas is preferred. In addition to oxygen gas, inert gases such as He and Ar, or CO, CO2, NH3, SO2, N2, NO2, and H2 gases can also be added. Gas etching can also be performed using only CO, CO2, NH3, N2, NO2, and H2 gases without oxygen gas. The latter gases are particularly preferred for sidewall protection to prevent undercutting of the pattern sidewalls.

[0265] On the other hand, gas etching is also preferably used for etching the intermediate layer in the three-layer process. The same gas etching as that described in the two-layer process above can be applied. In particular, the processing of the intermediate layer in the three-layer process is preferably performed using a fluorocarbon-based gas with the resist pattern as a mask. Then, as described above, the resist underlayer film can be processed by, for example, performing oxygen gas etching with the intermediate layer pattern as a mask.

[0266] When an inorganic hard mask intermediate layer film is formed as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not particularly limited, but for example, the methods described in JP 2002-334869 A (Patent Document 9) and WO 2004 / 066377 (Patent Document 10) can be used. A photoresist film can be formed directly on such an intermediate layer film, or an organic antireflective coating (BARC) can be formed on the intermediate layer film by spin coating, and then a photoresist film can be formed on top of that.

[0267] A polysilsesquioxane-based intermediate layer is also preferably used as the intermediate layer. By providing the resist intermediate layer with the effect of an anti-reflection film, reflection tends to be effectively suppressed. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but for example, those described in JP 2007-226170 A (Patent Document 11) and JP 2007-226204 A (Patent Document 12) can be used.

[0268] The subsequent etching of the substrate can also be performed by conventional methods. For example, if the substrate is SiO2 or SiN, etching can be performed primarily with fluorocarbon-based gases, and if it is p-Si, Al, or W, etching can be performed primarily with chlorine- or bromine-based gases. When etching the substrate with fluorocarbon-based gases, the silicon-containing resist in a two-layer resist process and the silicon-containing intermediate layer in a three-layer process are stripped simultaneously with substrate processing. On the other hand, when etching the substrate with chlorine- or bromine-based gases, the silicon-containing resist film or silicon-containing intermediate layer is stripped separately, and generally, dry etching stripping using fluorocarbon-based gases is performed after substrate processing.

[0269] The resist underlayer film of this embodiment is characterized by excellent substrate etching resistance. The substrate can be appropriately selected from known materials and includes, but is not limited to, Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc. The substrate may also be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such a film to be processed include, but are not limited to, various low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si. These films are typically made of a different material from the base material (support). The thickness of the substrate or film to be processed is not particularly limited, but is typically preferably about 50 to 1,000,000 nm, and more preferably 75 to 50,000 nm.

[0270] The composition of the present embodiment can be prepared by blending the components and mixing them using a stirrer, etc. Furthermore, when the composition of the present embodiment contains a filler or a pigment, it can be prepared by dispersing or mixing them using a dispersing device such as a dissolver, homogenizer, or three-roll mill. [Example]

[0271] Hereinafter, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples in any way.

[0272] (Measurement of Mn, Mw and Mw / Mn) The number average molecular weight (Mn), mass average molecular weight (Mw), and dispersity (Mw / Mn) were determined in terms of polystyrene by gel permeation chromatography (GPC) analysis under the following measurement conditions. Equipment: "Shodex GPC-101" (product name, manufactured by Showa Denko K.K.) Column: "KF-80M" x 3 (product name, manufactured by Showa Denko K.K.) Eluent: tetrahydrofuran (hereinafter also referred to as "THF") Flow rate: 1mL / min Temperature: 40℃

[0273] (Synthesis Example 1) Synthesis of R-BINL-2EO A 1-L four-neck flask with a bottomless opening, equipped with a Dimroth condenser, a thermometer, and a stirring blade, was prepared. 26.3 g (50 mmol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene (hereinafter abbreviated as "BINL-2EO"), 21.0 g of 40% by weight aqueous formaldehyde solution (280 mmol as formaldehyde, manufactured by Mitsubishi Gas Chemical Company, Inc.), and 0.97 mL of 98% by weight sulfuric acid (manufactured by Kanto Chemical Co., Inc.) were charged into the flask under a nitrogen stream and refluxed at 100°C for 7 hours. Subsequently, 180.0 g of ortho-xylene (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluent to the reaction solution. After allowing to stand, the lower aqueous phase was removed. Further, neutralization and washing with water were carried out, and ortho-xylene was distilled off under reduced pressure to obtain 18.0 g of a brown solid resin (R-BINL-2EO). Here, BINL-2EO was synthesized by a method similar to the synthesis method described in paragraph 0062 of WO 2019 / 044875. The Mw and Mw / Mn of the resulting resin (R-BINL-2EO) were measured by the above-mentioned method, and were found to be Mw=1300 and Mw / Mn=1.30.

[0274] [ka] [ka]

[0275] (Synthesis Example 2) Synthesis of R2-BINL-2EO The target compound (R2-BINL-2EO) represented by the following formula (R2-BINL-2EO) was obtained in the same manner as in Synthesis Example 1, except that 9.2 g (50 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of 21.0 g of a 40 mass % formaldehyde aqueous solution (280 mmol as formaldehyde, manufactured by Mitsubishi Gas Chemical Company, Inc.). The Mw and Mw / Mn of the resulting resin (R2-BINL-2EO) were measured by the above-mentioned method, and were found to be Mw=1410 and Mw / Mn=1.40.

[0276] [ka]

[0277] (Synthesis Example 3) Synthesis of R3-BINL-2EO A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 26.3 g (50 mmol) of BINL-2EO and 5 g (10 mmol) of copper monobutyl phthalate. 100 mL of 1-butanol was added as a solvent, and the reaction mixture was stirred at 100°C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The resulting solid was dried to obtain 19 g of the target resin (R3-BINL-2EO) with the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and was found to be Mn=920 and Mw / Mn=1.25.

[0278] [ka]

[0279] (Comparative Synthesis Example 1) Synthesis of C-1 A 10 L four-neck flask with a bottomless opening was prepared, equipped with a Dimroth condenser, a thermometer, and a stirring blade. 1.09 kg (7 mol, Mitsubishi Gas Chemical Company, Inc.) of 1,5-dimethylnaphthalene, 2.1 kg of 40% by weight formalin solution (28 mol as formaldehyde, Mitsubishi Gas Chemical Company, Inc.), and 0.97 mL of 98% by weight sulfuric acid (Kanto Chemical Co., Inc.) were charged into the flask under a nitrogen stream and refluxed at 100°C for 7 hours. Subsequently, 1.8 kg of ethylbenzene (Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a dilution solvent to the reaction solution. After allowing to stand, the lower aqueous phase was removed. The mixture was neutralized and washed with water. The ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin. The molecular weight of the obtained dimethylnaphthalene formaldehyde resin was a number average molecular weight (Mn): 562, a weight average molecular weight (Mw): 1168, and a dispersity (Mw / Mn): 2.08.

[0280] Next, a 0.5 L four-neck flask equipped with a Dimroth condenser, a thermometer, and a stirring blade was prepared. Under a nitrogen stream, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained above and 0.05 g of p-toluenesulfonic acid were charged into the four-neck flask. The temperature was raised to 190°C and heated for 2 hours, followed by stirring. 52.0 g (0.36 mol) of 1-naphthol was then added, and the temperature was raised to 220°C and reacted for 2 hours. After dilution with a solvent, the mixture was neutralized and washed with water. The solvent was then removed under reduced pressure to obtain 126.1 g of a dark brown solid resin (C-1). The resulting resin (C-1) had Mn: 885, Mw: 2220, and Mw / Mn: 2.51.

[0281] (Synthesis Example 1) Synthesis of AC-1 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to form a reaction solution. The reaction solution was polymerized for 22 hours under a nitrogen atmosphere at a reaction temperature of 63°C, and then added dropwise to 400 mL of n-hexane. The resulting resin was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40°C under reduced pressure to obtain AC-1, represented by the following formula:

[0282] [ka]

[0283] In formula AC-1, "40", "40", and "20" indicate the ratio of each structural unit, and do not indicate a block copolymer.

[0284] [Performance Evaluation of Resist Film-Forming Compositions: Examples 1-1 to 5-1, Comparative Example 1] Resist film-forming compositions having the formulations shown in Table 1 below were prepared using 6,6'-diphenyl-1,1'-bi-2,2'-naphthol (hereinafter abbreviated as "BINL") as the compound, BINL-2EO similar to that used in Synthesis Example 1, R-BINL-2EO obtained in Synthesis Example 1, and R2-BINL-2EO and R3-BINL-2EO obtained in Synthesis Examples 2 and 3. The acid generators, acid diffusion controllers, and organic solvents used were as follows. Acid generator: Triphenylsulfonium nonafluoromethanesulfonate manufactured by Midori Chemical Co., Ltd. (represented as "TPS-109" in the table). Acid diffusion controller: Tri-n-octylamine manufactured by Kanto Chemical Co., Ltd. (represented as "TOA" in the table). Crosslinker: Nikalac MW-100LM manufactured by Sanwa Chemical Co., Ltd. (represented as "MW-100LM" in the table). Organic solvent: Propylene glycol monomethyl ether manufactured by Kanto Chemical Co., Ltd. (represented as "PGME" in the table).

[0285] [ka] [ka]

[0286] [Table 1]

[0287] [Evaluation method] (1) Safe solvent solubility test for compounds or resins The solubility of a compound or resin in PGME, PGMEA, and CHN was evaluated based on the amount dissolved in each solvent according to the following criteria. The amount dissolved was measured at 23°C by precisely weighing the compound or resin alone into a test tube, adding the target solvent to a predetermined concentration, applying ultrasound in an ultrasonic cleaner for 30 minutes, and then visually observing the state of the liquid. A: 5.0% by mass or less dissolved amount B: 2.0% by mass or less dissolved amount < 5.0% by mass C: dissolved amount < 2.0% by mass

[0288] (2) Storage stability of the resist film-forming composition The storage stability of a resist film-forming composition containing a compound or resin was evaluated by preparing the resist film-forming composition, leaving it at 23°C for 3 days, and visually observing whether or not precipitation occurred. The resist film-forming composition was spin-coated on a clean silicon wafer and then pre-exposure baked (PB) on a hot plate at 110°C to form a 50 nm thick resist film. The resist film-forming composition was rated C if precipitation occurred, B if the solution was homogeneous but the thin film had defects, and A if the solution was homogeneous, the thin film was free of defects, and thin film formation was satisfactory.

[0289] (3) Resist pattern and sensitivity The resist film obtained in (2) above was irradiated with an electron beam using an electron beam lithography system (ELS-7500, manufactured by Elionix Co., Ltd.) in a line-and-space configuration with 50 nm spacing and a 1:1 ratio. After irradiation, the resist film was heated at 110°C for 90 seconds and developed by immersing it in an alkaline developer containing 2.38% by mass of TMAH for 60 seconds. The resist film was then washed with ultrapure water for 30 seconds and dried to form a resist pattern. The shape of the resulting 50 nm L / S (1:1) resist pattern was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. Regarding the resist pattern shape after development, a resist pattern without pattern collapse and with better rectangularity than Comparative Example 1 was evaluated as A, and a resist pattern equivalent to or inferior to Comparative Example 1 was evaluated as C. Furthermore, the minimum electron beam energy amount capable of drawing a good pattern shape was evaluated as sensitivity. That is, those that were 10% or more better than Comparative Example 1 were rated A, those that were less than 10% better were rated B, and those that were the same as or worse than Comparative Example 1 were rated C.

[0290] (4) Etching resistance Etching equipment: RIE-10NR manufactured by Samco International, output: 50 W, pressure: 20 Pa, time: 2 min, etching gas: Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm). An etching test was conducted on the resist film obtained in (2) above using the etching equipment and conditions described above, and the etching rate was measured. Then, the etching resistance was evaluated using the etching rate of a resist film prepared using novolac ("PSM4357" manufactured by Gunei Chemical Co., Ltd.) as the standard, according to the following evaluation criteria: A: Etching rate less than -15% compared to novolac resist film B: Etching rate -15% to +5% compared to novolac resist film C: Etching rate more than +5% compared to novolac resist film

[0291] The solubility of each compound or resin used in Examples 1-1 to 5-1 and Comparative Example 1 in a safe solvent was evaluated by the above-mentioned method, and the results are shown in Table 2. Furthermore, Table 2 shows the evaluation results of the resist film-forming compositions of Examples 1-1 to 5-1 and Comparative Example 1 using the methods described above.

[0292] [Table 2]

[0293] [Performance Evaluation of Compositions for Forming Resist Underlayer Film: Examples 1-2 to 5-2, Comparative Example 2] Compositions for forming resist underlayer films were prepared according to the formulations shown in Table 3. These compositions for forming resist underlayer films were then spin-coated onto silicon substrates, followed by baking at 240°C for 60 seconds and then at 400°C for 120 seconds to produce resist underlayer films with a thickness of 200 nm. The acid generators, crosslinkers, and organic solvents used were as follows: Acid generator: di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (referred to as "DTDPI" in the table) (manufactured by Midori Chemical Co., Ltd.) Crosslinking agent: "Nicalac MX270" (referred to as "MX270" in the table) (product name, manufactured by Sanwa Chemical Co., Ltd.) Organic solvent: Propylene glycol monomethyl ether acetate (also referred to as "PGMEA" in the table) Subsequently, the etching resistance was evaluated by the same method as in (4) Etching Resistance above for the compositions for forming resist underlayer films of Examples 1-2 to 5-2 and Comparative Example 2. The results are also shown in Table 3.

[0294] [Table 3]

[0295] (Examples 1-3 to 5-3) Each of the resist underlayer film-forming compositions prepared in Examples 1-3 to 5-3 above was applied to a 300 nm-thick SiO2 substrate and baked at 240°C for 60 seconds and then at 400°C for 120 seconds to form a 70 nm-thick resist underlayer film. An ArF resist solution was applied to this resist underlayer film and baked at 130°C for 60 seconds to form a 140 nm-thick photoresist film. The ArF resist solution used was prepared by blending 5 parts by mass of the resin (AC-1) of Synthesis Example, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA.

[0296] Next, the photoresist film was exposed to light using an electron beam lithography system "ELS-7500" (product name, manufactured by Elionix Co., Ltd., 50 keV), baked at 115°C for 90 seconds (PEB), and developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds to obtain a positive resist pattern.

[0297] The results of observing defects in the resulting resist patterns of 55 nmL / S (1:1) and 80 nmL / S (1:1) are shown in Table 4. In the table, "Good" in the results of "Resist pattern after development" indicates that no pattern collapse was observed in the formed resist pattern, and "Bad" indicates that pattern collapse was observed in the formed resist pattern. Furthermore, as a result of the above observation, the minimum line width at which there was no pattern collapse and good rectangularity was used as an index of evaluation as "resolution." Furthermore, the minimum amount of electron beam energy capable of drawing a good pattern shape was used as an index of evaluation as "sensitivity." The results are shown in Table 4.

[0298] (Comparative Example 3) A photoresist film was formed directly on an SiO2 substrate in the same manner as in Example 1-3, except that no underlayer film was formed, and a positive resist pattern was obtained. The results are shown in Table 4.

[0299] [Table 4]

[0300] (Examples 1-4 to 5-4) Each of the resist underlayer film-forming compositions of Examples 1-4 to 5-4 was applied to a 300 nm thick SiO2 substrate and baked at 240°C for 60 seconds and then at 400°C for 120 seconds to form a resist underlayer film with a thickness of 80 nm. A silicon-containing intermediate layer material was applied to the resist underlayer film and baked at 200°C for 60 seconds to form a 35 nm thick intermediate layer film. The ArF resist solution was then applied to the intermediate layer film and baked at 130°C for 60 seconds to form a 150 nm thick photoresist film. The silicon-containing intermediate layer material used was the silicon-containing polymer described in Synthesis Example 1 of JP 2007-226170 A. Next, the photoresist film was exposed to light using a mask using an electron beam lithography system (Elionix; ELS-7500, 50 keV), baked at 115 °C for 90 seconds (PEB), and developed with a 2.38 mass% tetramethylammonium hydroxide (hereinafter also referred to as "TMAH") aqueous solution for 60 seconds to obtain a 55 nmL / S (1:1) positive resist pattern. Then, using a parallel plate RIE system "RIE-10NR" (trade name, manufactured by Samco International) to dry etch the silicon-containing intermediate layer film using the resulting resist pattern as a mask, followed by dry etching the resist underlayer film using the resulting silicon-containing intermediate layer film pattern as a mask, and then dry etching the SiO2 film using the resulting resist underlayer film pattern as a mask.

[0301] The etching conditions for each are as follows: Etching conditions for resist pattern onto resist intermediate layer film Output: 50W Pressure: 20Pa Time: 1 min Etching gas Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:8:2 (sccm) Etching conditions for resist intermediate film pattern onto resist underlayer film Output: 50W Pressure: 20Pa Time: 2 min Etching gas Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm) Etching conditions for resist underlayer film pattern onto SiO2 film Output: 50W Pressure: 20Pa Time: 2 min Etching gas Ar gas flow rate: C5F 12 Gas flow rate: C2F6 gas flow rate: O2 gas flow rate =50:4:3:1(sccm)

[0302] The cross section of the pattern obtained as described above (i.e., the shape of the SiO2 film after etching) was observed using an electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.) to evaluate the resist pattern formability. The observation results are shown in Table 5. In the table, "good" under "resist pattern formability" indicates that no major defects were observed in the cross section of the formed pattern, and "poor" indicates that major defects were observed in the cross section of the formed pattern.

[0303] [Table 5]

[0304] As is clear from the above, the composition of the present embodiment simultaneously satisfies high levels of solubility in organic solvents, etching resistance, and resist pattern formability when used for forming a lithography film, and is therefore useful for forming a lithography film.

[0305] (Synthesis Example A1) Synthesis of R-PPPBP A 1-L four-neck flask with a bottomless opening was prepared, equipped with a Dimroth condenser, a thermometer, and a stirring blade. In a nitrogen stream, 19.7 g (50 mmol) of the compound (PPPBP) obtained by the method described in Synthesis Example 1 of International Publication WO 2011 / 090022, 21.0 g of a 40% by weight aqueous formaldehyde solution (280 mmol as formaldehyde, manufactured by Mitsubishi Gas Chemical Company, Inc.), and 0.97 mL of 98% by weight sulfuric acid (manufactured by Kanto Chemical Co., Inc.) were charged into the four-neck flask. The mixture was refluxed at 100°C under atmospheric pressure for 7 hours. Subsequently, 180.0 g of ortho-xylene (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added as a dilution solvent. After allowing to stand, the lower aqueous phase was removed. The mixture was neutralized and washed with water. The ortho-xylene was removed by distillation under reduced pressure, yielding 12.8 g of a brown solid resin (R-PPPBP). The resulting resin (R-PPPBP) had an Mw of 1570 and an Mw / Mn of 1.35.

[0306] [ka]

[0307] [ka]

[0308] (Synthesis Example A2) Synthesis of R2-PPPBP Synthesis was performed in the same manner as in Synthesis Example 1, except that 9.2 g (50 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of 21.0 g of a 40 mass % formaldehyde aqueous solution (280 mmol as formaldehyde, manufactured by Mitsubishi Gas Chemical Company, Inc.), to obtain the target compound (R2-PPPBP) represented by the following formula (R2-PPPBP). The Mw and Mw / Mn of the resulting resin (R2-PPPBP) were measured by the above-mentioned method, and were found to be Mw=1600 and Mw / Mn=1.45.

[0309] [ka]

[0310] (Synthesis Example A3) Synthesis of R3-PPPBP A 500 mL vessel equipped with a stirrer, condenser, and burette was charged with 19.7 g (50 mmol) of PPPBP and 5 g (10 mmol) of copper monobutyl phthalate. 100 mL of 1-butanol was added as a solvent, and the reaction mixture was stirred at 100°C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The resulting solid was dried to obtain the target resin (R3-PPPBP) with the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and was found to be Mn=1100 and Mw / Mn=1.30.

[0311] [ka]

[0312] (Comparative Synthesis Example A1) Synthesis of C-1 A 10 L four-neck flask with a bottomless opening was prepared, equipped with a Dimroth condenser, a thermometer, and a stirring blade. 1.09 kg (7 mol, Mitsubishi Gas Chemical Company, Inc.) of 1,5-dimethylnaphthalene, 2.1 kg of 40% by weight formalin solution (28 mol as formaldehyde, Mitsubishi Gas Chemical Company, Inc.), and 0.97 mL of 98% by weight sulfuric acid (Kanto Chemical Co., Inc.) were charged into the flask under a nitrogen stream and refluxed at 100°C for 7 hours. Subsequently, 1.8 kg of ethylbenzene (Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a dilution solvent to the reaction solution. After allowing to stand, the lower aqueous phase was removed. The mixture was neutralized and washed with water. The ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin. The resulting dimethylnaphthalene formaldehyde resin had an Mn of 562, an Mw of 1168, and an Mw / Mn of 2.08.

[0313] Next, a 0.5 L four-neck flask equipped with a Dimroth condenser, thermometer, and stirring blade was prepared. Under a nitrogen stream, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged into the four-neck flask. The temperature was raised to 190°C and heated for 2 hours, followed by stirring. 52.0 g (0.36 mol) of 1-naphthol was then added, and the temperature was raised to 220°C and the reaction was continued for 2 hours. After dilution with a solvent, the mixture was neutralized and washed with water. The solvent was then removed under reduced pressure to obtain 126.1 g of a dark brown solid resin (C-1). The representative partial structure of resin (C-1) is shown below. These partial structures are bonded via methylene groups, but some are also bonded via ether bonds. The resulting resin (C-1) had an Mn of 885, an Mw of 2220, and an Mw / Mn ratio of 2.51. [ka]

[0314] (Synthesis Example A1) Synthesis of AC-1 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to form a reaction solution. The reaction solution was polymerized for 22 hours under a nitrogen atmosphere at a reaction temperature of 63°C, and then added dropwise to 400 mL of n-hexane. The resulting resin was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40°C under reduced pressure to obtain AC-1, represented by the following formula:

[0315] [ka]

[0316] In formula AC-1, "40", "40", and "20" indicate the ratio of each structural unit, and do not indicate a block copolymer.

[0317] [Performance evaluation of the composition for forming a resist film] (Examples A1-1 to A5-1 and Comparative Example A1) Lithography film-forming compositions (resist film-forming compositions) having the compositions shown in Table 6 were prepared using the compound (PPPBP, structural formula as described above) obtained by the method described in Synthesis Example 1 of International Publication WO2011 / 090022, the compound (BisP-IST-NMe) obtained by the method described in Synthesis Example 5 of International Publication WO2011 / 090022, the resins (R-PPPBP, R2-PPPBP, R3-PPPBP) obtained in Synthesis Examples A1 to A4, and the resin (C-1) obtained in Synthesis Comparative Example A1. The acid generator, acid diffusion controller, crosslinker, and organic solvent used were as follows. In Table 6, the numbers in parentheses indicate the blend amounts (parts by mass). Acid generator: triphenylsulfonium trifluoromethanesulfonate (TPS-109 (trade name), manufactured by Midori Chemical Co., Ltd.) Acid diffusion controller: tri-n-octylamine (TOA, manufactured by Kanto Chemical Co., Ltd.) Crosslinking agent: Nikalac MW-100LM (MW-100LM, product name, manufactured by Sanwa Chemical Co., Ltd.) Organic solvent: propylene glycol monomethyl ether (PGME, manufactured by Kanto Chemical Co., Ltd.)

[0318] [ka]

[0319] [Table 6]

[0320] [Evaluation method] (1) Solubility in safe solvents The solubility of compound (PPPBP), compound (BisP-IST-NMe), resins (R-PPPBP, R2-PPPBP, R3-PPPBP, R4-PPPBP), and resin (C-1) in PGME (Kanto Chemical Co., Ltd.), PGMEA (Kanto Chemical Co., Ltd.), and CHN (Kanto Chemical Co., Ltd.) was evaluated. Specifically, the solubility was evaluated based on the amount dissolved in each solvent according to the following criteria. The amount dissolved was measured at 23°C by precisely weighing the compound or resin separately into a test tube, adding the target solvent to a predetermined concentration, applying ultrasound in an ultrasonic cleaner for 30 minutes, and then visually observing the state of the liquid. A:5.0 mass%≦dissolution amount B:2.0 mass%≦dissolved amount<5.0 mass% C: Dissolved amount <2.0% by mass

[0321] (2) Storage stability and thin film formation of the resist film-forming composition The storage stability of the resist film-forming compositions was evaluated by preparing each resist film-forming composition according to the formulations listed in Table 6, allowing it to stand at 23°C for three days, and visually observing whether or not precipitation occurred. After allowing it to stand for three days, the resist film-forming composition was evaluated as ◯ if it was a homogeneous solution with no precipitation, and x if precipitation occurred. Furthermore, the homogeneous resist film-forming composition was spin-coated on a clean silicon wafer, and then pre-exposure baked (PB) in an oven at 110°C to form a 40 nm thick resist film. The resist film thus formed was evaluated as ◯ if the thin film formation was good, and x if the formed film had defects.

[0322] (3) Resist pattern Each resist film obtained by the evaluation method (2) was irradiated with an electron beam using an electron beam lithography system (ELS-7500, manufactured by Elionix Co., Ltd., 50 keV) in a 1:1 line and space setting with 50 nm spacing. After irradiation, the resist films were heated at 110°C for 90 seconds and then developed by immersion in an alkaline developer containing 2.38% by mass of tetramethylammonium hydroxide (TMAH) for 60 seconds. Each resist film was then washed with ultrapure water for 30 seconds and dried to form a resist pattern. The shape of the resulting L / S (1:1) resist pattern with 50 nm spacing was observed using an electron microscope (S-4800, product name) manufactured by Hitachi, Ltd. Regarding the resist pattern shape after development, a resist pattern with no pattern collapse and better rectangularity than Comparative Example A1 was evaluated as A, and a resist pattern with the same or inferior rectangularity to Comparative Example A1 was evaluated as C. Note that in Comparative Example A1, the resist pattern shape after development showed pattern collapse and poor rectangularity. Furthermore, for good pattern shapes, sensitivity was evaluated using a stepwise method with the minimum electron beam energy amount capable of being written. That is, a minimum electron beam energy amount 10% or more better than Comparative Example A1 was evaluated as S, a minimum electron beam energy amount less than 10% but better than Comparative Example A1 was evaluated as A, and a minimum electron beam energy amount equal to or worse than Comparative Example A1 was evaluated as C.

[0323] (4) Etching resistance An etching test was performed under the following conditions for each resist film obtained by the evaluation method (2) described above, and the etching rate was measured. Furthermore, a resist film was prepared in the same manner as the evaluation method (2) described above, using a composition obtained by substituting a novolak resin (PSM4357 (model number) manufactured by Gunei Chemical Industry Co., Ltd.) for the PPPBP of Example A1-1 in the composition shown in Table 6, and an etching test was also performed on this resist film under the following conditions. The etching resistance of each resist film was evaluated according to the following evaluation criteria, using the etching rate of the resist film obtained using the novolak resin as the standard. (Etching conditions) Etching equipment: Samco Corporation RIE-10NR (product name) Output: 50W Pressure: 20Pa Time: 2 min Etching gas: Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm) (Evaluation criteria) A: The etching rate is less than -15% compared to novolac resin resist films. B: The etching rate is −15% to +5% compared to the novolac resin resist film. C: The etching rate is more than +5% compared to the novolac resin resist film.

[0324] The evaluation results are shown in Table 7. In Table 7, the solubility of each of the compound (PPPBP), the compound (BisP-IST-NMe), the resin (R-PPPBP), and the resin (C-1) in each solvent is shown for Example A1-1, Example A2-1, Example A3-1, and Comparative Example A1, respectively.

[0325] [Table 7]

[0326] [Performance evaluation of the composition for forming the resist underlayer film] (Examples A1-2 to A5-2 and Comparative Example 2) Using the compound (PPPBP), the compound (BisP-IST-NMe), the resins (R-PPPBP, R2-PPPBP, R3-PPPBP), and the resin (C-1), compositions for forming lithography films (compositions for forming resist underlayer films) were prepared, each having the composition shown in Table 8. The acid generators, crosslinkers, and organic solvents used were as follows. In Table 8, the numbers in parentheses indicate the blend amounts (parts by mass). Acid generator: di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI, manufactured by Midori Chemical Co., Ltd.) Crosslinking agent: Nikalac MX270 (MX270, product name, manufactured by Sanwa Chemical Co., Ltd.) Organic solvent: propylene glycol monomethyl ether acetate (PGMEA, manufactured by Kanto Chemical Co., Ltd.)

[0327] Subsequently, these resist underlayer film-forming compositions or novolak resin (PSM4357 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) were spin-coated onto silicon substrates, which were then heated at 240°C for 60 seconds and further baked at 400°C for 120 seconds to produce resist underlayer films with a thickness of 200 nm. The resulting resist underlayer films were each subjected to an etching test under the etching conditions described in the evaluation method (4) above. In addition, a composition was prepared using a novolak resin instead of PPPBP in Example A1-2 in the formulation shown in Table 8, and the etching resistance of each resist film was evaluated according to the following evaluation criteria, using the etching rate of the resist underlayer film obtained using this composition as the standard. (Evaluation criteria) A: The etching rate is less than -15% compared to the resist underlayer film of novolac resin. B: The etching rate is −15% to +5% compared to the resist underlayer film of novolac resin. C: The etching rate is more than +5% compared to the resist underlayer film of novolac resin. The results of these evaluations are shown in Table 8.

[0328] [Table 8]

[0329] (Examples A1-3 to A5-3) Each of the resist underlayer film-forming compositions prepared in Examples A1-2 to A5-2 was applied to a 300 nm-thick SiO2 substrate, heated at 240°C for 60 seconds, and then baked at 400°C for 120 seconds to form a 70 nm-thick resist underlayer film. ArF excimer laser resist solution A was applied to the resist underlayer film and baked at 130°C for 60 seconds to form a 140 nm-thick photoresist film. The ArF excimer laser resist solution A was prepared by blending 5 parts by mass of the resin (AC-1) obtained in Synthesis Example A1, 1 part by mass of triphenylsulfonium trifluoromethanesulfonate (TPS-109 (trade name), manufactured by Midori Chemical Co., Ltd.), 2 parts by mass of tributylamine (manufactured by Kanto Chemical Co., Ltd.), and 92 parts by mass of PGMEA (manufactured by Kanto Chemical Co., Ltd.).

[0330] Next, using an electron beam lithography system (ELS-7500, manufactured by Elionix, Inc., 50 keV), the photoresist films formed on the obtained resist underlayer films were exposed to electron beams in a 1:1 line-and-space setting with 55 nm and 80 nm spacing. After that, the resist films were baked (PEB) at 115°C for 90 seconds, and then developed by immersion in an alkaline developer containing 2.38% by mass of tetramethylammonium hydroxide for 60 seconds, thereby obtaining positive resist patterns (1).

[0331] The resulting resist pattern with an L / S (1:1) spacing of 55 nm and the resist pattern with an L / S (1:1) spacing of 80 nm were used to observe defects using an electron microscope (S-4800 (trade name), manufactured by Hitachi, Ltd.). The results are shown in Table 9. In Table 9, "good" indicates that no pattern collapse was observed in the formed resist pattern, and "poor" indicates that pattern collapse was observed in the formed resist pattern. Furthermore, the minimum electron beam energy amount that allows drawing of a good pattern shape was measured and evaluated as sensitivity.

[0332] (Comparative example A3) Positive resist patterns were obtained in the same manner as in Examples A1-3 to A5-3, except that a photoresist film was directly formed on a 300-nm-thick SiO2 substrate using ArF excimer laser resist solution A without forming a resist underlayer film. Thereafter, defects in the resulting 55-nm-spaced L / S (1:1) resist pattern and the 80-nm-spaced L / S (1:1) resist pattern obtained in the same manner as in Examples A1-3 to A5-3 were observed using an electron microscope (S-4800 (trade name), manufactured by Hitachi, Ltd.). Furthermore, the minimum electron beam energy amount that allows drawing of a good pattern shape was measured and evaluated as sensitivity.

[0333] The results are shown in Table 9.

[0334] [Table 9]

[0335] (Examples A1-4 to A5-4) The resist underlayer film-forming compositions prepared in Examples A1-2 to A5-2 were each applied to a 300 nm-thick SiO2 substrate, heated at 240°C for 60 seconds, and baked at 400°C for 120 seconds to form an 80 nm-thick resist underlayer film. A silicon-containing intermediate layer material was applied to the resist underlayer film and baked at 200°C for 60 seconds to form a 35 nm-thick silicon-containing intermediate layer film. Furthermore, the ArF excimer laser resist solution A was applied to the silicon-containing intermediate layer film and baked at 130°C for 60 seconds to form a 150 nm-thick photoresist film. The silicon-containing intermediate layer material used was the silicon-containing polymer described in Synthesis Example 1 of JP 2007-226170 A.

[0336] Next, using an electron beam lithography system (ELS-7500, manufactured by Elionix Co., Ltd., 50 keV), the photoresist film formed on the resulting silicon-containing intermediate layer was irradiated with an electron beam in a 1:1 line-and-space setting with 55 nm spacing, and exposed to a pattern to be used as a mask for dry etching. The resist was then baked (PEB) at 115°C for 90 seconds, and developed by immersion in an alkaline developer containing 2.38% by mass of tetramethylammonium hydroxide for 60 seconds, yielding a positive resist pattern with a 55 nm spacing of L / S (1:1). Thereafter, using an etching apparatus (parallel plate type RIE apparatus, RIE-10NR (trade name), manufactured by Samco Corporation), dry etching processing of the silicon-containing intermediate layer film was performed using the obtained resist pattern as a mask under the following conditions, followed by dry etching processing of the resist underlayer film using the obtained silicon-containing intermediate layer film pattern as a mask, followed by dry etching processing of the SiO2 film using the obtained resist underlayer film pattern as a mask.

[0337] The etching conditions for each are as follows: Etching conditions for silicon-containing intermediate layer films Output: 50W Pressure: 20Pa Time: 1 min Etching gas: Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:8:2 (sccm) Etching conditions for resist underlayer film Output: 50W Pressure: 20Pa Time: 2 min Etching gas: Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm) Etching conditions for SiO2 film Output: 50W Pressure: 20Pa Time: 2 min Etching gas: Ar gas Flow rate: CF 12 Gas flow rate: C2F6 gas flow rate: O2 gas flow rate = 50:4:3:1 (sccm)

[0338] The cross section of the pattern obtained as described above (i.e., the shape of the SiO2 substrate after etching) was observed using an electron microscope (S-4800 (product name), manufactured by Hitachi, Ltd.) to evaluate the resist pattern formability. The observation results are shown in Table 10. In the table, "good" indicates that no major defects were observed in the cross section of the formed pattern, and "poor" indicates that major defects were observed in the cross section of the formed pattern.

[0339] [Table 10]

[0340] As shown in Tables 6 to 10, according to this embodiment, it is possible to provide a composition that is useful as a film-forming material for lithography, which has high solubility in organic solvents, excellent storage stability and thin-film formability, high etching resistance, high sensitivity, and excellent resist pattern formability, and which satisfies these physical properties in a well-balanced manner at a high level.

[0341] This application is based on a Japanese patent application (Patent Application No. 2020-118023) filed with the Japan Patent Office on July 8, 2020, and a Japanese patent application (Patent Application No. 2020-135055) filed with the Japan Patent Office on August 7, 2020, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0342] The first composition has high heat resistance and high solvent solubility, making it suitable for wet processes. The second composition has high solubility in organic solvents, excellent storage stability and thin-film formability, high etching resistance, high sensitivity, and excellent resist pattern formability, satisfying these physical properties in a well-balanced manner at a high level, making it possible to provide a composition useful as a film-forming material for lithography. Furthermore, the composition of the present invention has excellent heat resistance and high solubility in solvents, making it suitable for wet processes. Therefore, the film-forming material for lithography using the composition of the present invention and the lithography film formed therefrom can be widely and effectively used in various applications requiring these properties. Therefore, the present invention can be widely and effectively used in, for example, electrical insulating materials, resist resins, semiconductor sealing resins, adhesives for printed wiring boards, electrical laminates used in electrical equipment, electronic devices, industrial equipment, etc., matrix resins for prepregs used in electrical equipment, electronic devices, industrial equipment, etc., build-up laminate materials, resins for fiber-reinforced plastics, sealing resins for liquid crystal display panels, paints, various coating agents, adhesives, semiconductor coating agents, semiconductor resist resins, resins for forming resist underlayer films, etc. In particular, the present invention can be particularly effectively used in the field of lithography films.

Claims

1. A composition for forming a lithographic film, comprising at least one compound selected from a compound represented by general formula (1), a compound represented by general formula (3), a compound represented by formula (4), a compound represented by formula (5), and a resin obtained using these as a monomer. 【Chemistry 1】 (In the formula, each R independently represents an aromatic group having 6 to 36 carbon atoms, which may have a substituent or a heteroatom; X's each independently represent an alkanediyl group having 2 to 4 carbon atoms or an alkanediylcarbonyl group having 1 to 4 carbon atoms, each of which may have a substituent; P's each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, each of which may have a substituent, or a hydrogen atom, a crosslinkable group, or a dissociable group; Each m independently represents an integer of 1 to 6, and each n independently represents an integer of 0 to 4. 【Chemistry 2】 (In the formula, each R independently represents an aromatic group having 6 to 36 carbon atoms, which may have a substituent or a heteroatom; R c each independently represents a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, or an arylene group having 1 to 20 carbon atoms which may have a substituent, X's each independently represent an alkanediyl group having 2 to 4 carbon atoms or an alkanediylcarbonyl group having 1 to 4 carbon atoms, each of which may have a substituent; P's each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, each of which may have a substituent, or a hydrogen atom, a crosslinkable group, or a dissociable group; Each m independently represents an integer of 1 to 6, and each n independently represents an integer of 0 to 4. 【Transformation 3】 (In formula (4), Each A independently represents an aromatic group having 6 to 10 carbon atoms; each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group; R 1 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Rx 1 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; Ry 1 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; m represents an integer of 0 to 4, and n represents an integer of 0 to 4. 【Chemistry 4】 (In formula (5), Each A independently represents an aromatic group having 6 to 10 carbon atoms; each P independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a crosslinkable group, or a dissociable group; R 2 represents an aromatic substituent having 6 to 10 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Rx 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; Ry 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom; m represents an integer of 0 to 4, and n represents an integer of 0 to 4.

2. 2. The composition for forming a lithographic film according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (2): 【Transformation 5】 (In the formula, R, X, P, and n are defined as in formula (1) above.)

3. The composition for forming a lithographic film according to claim 1 , comprising a compound represented by the general formula (3).

4. 2. The composition for forming a lithographic film according to claim 1, comprising at least one selected from the group consisting of a compound represented by formula (4), a compound represented by formula (5), and a resin obtained using these as a monomer.

5. The compound represented by formula (4) is a compound represented by formula (6), The composition for forming a lithographic film according to claim 4 , wherein the compound represented by formula (5) is a compound represented by formula (7): 【Transformation 6】 (In formula (6), P.R. 1 , Rx 1 , Ry 1 , m, and n are the same as those in formula (4). 【Transformation 7】 (In formula (7), P.R. 2 , Rx 2 , Ry 2 , m, and n are the same as those in formula (5).

6. The lithography film-forming composition according to claim 4 , wherein the resin is a resin represented by formula (8): 【Transformation 8】 (In formula (8), B is a structural unit derived from a compound represented by formula (4) and / or a structural unit derived from a compound represented by formula (5), L represents a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, or an arylene group having 1 to 20 carbon atoms which may have a substituent; When there are a plurality of B and / or L, they are independent of each other.

7. The lithographic film-forming composition according to any one of claims 1 to 6, further comprising a solvent.

8. The lithographic film-forming composition according to any one of claims 1 to 7, further comprising an acid generator.

9. The lithographic film-forming composition according to any one of claims 1 to 8, further comprising a crosslinking agent.

10. a photoresist layer forming step of forming a photoresist layer on a substrate using the lithography film-forming composition according to any one of claims 1 to 9; a developing step of irradiating predetermined regions of the photoresist layer with radiation and developing the layer to obtain a resist pattern; A method for forming a resist pattern, comprising:

11. 11. The method for forming a resist pattern according to claim 10, wherein the resist pattern is an insulating film pattern.

12. a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition for lithography film formation according to any one of claims 1 to 9; a photoresist layer forming step of forming at least one photoresist layer on the resist underlayer film; a developing step of irradiating predetermined regions of the photoresist layer with radiation and developing the layer to obtain a resist pattern; A method for forming a resist pattern, comprising:

13. a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition for lithography film formation according to any one of claims 1 to 9; an intermediate layer film forming step of forming an intermediate layer film on the resist underlayer film; a photoresist layer forming step of forming at least one photoresist layer on the intermediate layer film; a resist pattern forming step of irradiating predetermined regions of the photoresist layer formed in the photoresist layer forming step with radiation and developing the photoresist layer to obtain a resist pattern; an intermediate layer film pattern forming step of etching the intermediate layer film using the resist pattern as a mask to obtain an intermediate layer film pattern; a resist underlayer film pattern formation step of etching the resist underlayer film using the intermediate layer film pattern as a mask to obtain a resist underlayer film pattern; a substrate pattern forming step of etching the substrate using the resist underlayer film pattern as a mask to obtain a substrate pattern; A circuit pattern forming method comprising:

Images